Antibacterial and antiviral agents

Abstract

To provide an antibacterial antiviral agent which shows excellent antibacterial activity and antiviral activity while maintaining mechanical strength of a molded article, and which is capable of sustaining the antibacterial activity and the antiviral activity.SOLUTION: An antibacterial antiviral agent (Z) contains: a block polymer (A) having, as a constitutional unit, a block of hydrophobic polymer (a) and a block of hydrophilic polymer (b); and sulfonate (S). A resin composition (Y) contains the antibacterial antiviral agent (Z) and thermoplastic resin (E).SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to an antibacterial and antiviral agent. [Background technology]

[0002] Conventionally, antibacterial agents have been added to resins to impart antibacterial properties in response to hygiene needs, etc. Known antibacterial agents that can be added include inorganic antibacterial agents such as silver, copper, and zinc zeolites (see Patent Document 1). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Publication No. 6-116458 Summary of the Invention [Problem to be solved by the invention]

[0004] However, the technique of Patent Document 1 is not fully satisfactory in terms of the mechanical strength of the molded product, and improvements have been desired. An object of the present invention is to provide an antibacterial and antiviral agent that exhibits excellent antibacterial and antiviral properties while maintaining the mechanical strength of a molded article, and that can sustain the antibacterial and antiviral properties. [Means for solving the problem]

[0005] The present inventors have conducted extensive research to solve the above problems and have arrived at the present invention. Specifically, the present invention relates to an antibacterial and antiviral agent (Z) comprising a block polymer (A) having, as structural units, a block of a hydrophobic polymer (a) and a block of a hydrophilic polymer (b), and a sulfonate (S). [Effects of the Invention]

[0006] The antibacterial and antiviral agent (Z) of the present invention has the following effects. (1) It provides thermoplastic resins with antibacterial properties and their durability. (2) Imparting antiviral properties and their persistence to thermoplastic resins. (3) Molded articles of resin compositions containing the antibacterial and antiviral agent and thermoplastic resins have excellent mechanical strength. DETAILED DESCRIPTION OF THE INVENTION

[0007] <Hydrophobic polymer (a)> Examples of the hydrophobic polymer (a) in the present invention include polyamide (a1), polyolefin (a2), and polyester (a3). Among the above hydrophobic polymers (a), from the viewpoints of mechanical strength, antibacterial properties, and antiviral properties, polyamide (a1), polyolefin (a2), and polyester (a3) ​​are preferred, polyamide (a1) and polyolefin (a2) are more preferred, and polyolefin (a2) is particularly preferred. The hydrophobic polymer (a) in the present invention is preferably 1×10 11 It is a polymer with a volume resistivity exceeding Ω·cm. The volume resistivity in the present invention is a value obtained by measurement in an atmosphere of 23° C. and 50% RH in accordance with ASTM D257 (1984). The above (a) may be used alone or in combination of two or more.

[0008] <Polyamide (a1)> The polyamide (a1) in the present invention may be one obtained by ring-opening polymerization or polycondensation of an amide-forming monomer (a10). Examples of the amide-forming monomer (a10) include lactams (a101) and aminocarboxylic acids (a102). The amide-forming monomer (a10) may also be a combination of a diamine (a103) and a dicarboxylic acid (a104). Specifically, examples of the polyamide (a1) include lactam (a101), ring-opening polymerization or polycondensation of aminocarboxylic acid (a102), and polycondensation of diamine (a103) and dicarboxylic acid (a104).

[0009] Examples of the lactam (a101) include lactams having 4 to 20 carbon atoms (hereinafter sometimes abbreviated as C) (γ-lactam, δ-lactam, ε-caprolactam, enantholactam, capryllactam, ω-laurolactam, undecanolactam, etc.). Examples of ring-opening polymers of lactam (a101) include nylon 4, nylon 5, nylon 6, nylon 7, nylon 8, nylon 11, and nylon 12.

[0010] Examples of the aminocarboxylic acid (a102) include C6-12 aminocarboxylic acids (for example, ω-aminocaproic acid, ω-aminoenanthic acid, ω-aminocaprylic acid, ω-aminopelargonic acid, ω-aminocapric acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, and mixtures thereof).

[0011] The diamine (a103) may be a C2-40 diamine, such as an aliphatic, alicyclic, or aromatic (aliphatic) diamine, or a mixture thereof. Examples of the aliphatic diamine include C2 to C40 aliphatic diamines (for example, ethylenediamine, propylenediamine, hexamethylenediamine, decamethylenediamine, 1,12-dodecanediamine, 1,18-octadecanediamine, and 1,20-eicosanediamine). Examples of the alicyclic diamine include C5 to C40 alicyclic diamines (for example, 1,3- or 1,4-cyclohexanediamine, isophoronediamine, 4,4'-diaminocyclohexylmethane, and 2,2-bis(4-aminocyclohexyl)propane). Examples of aromatic diamines include C6 to C40 aromatic diamines (for example, p-phenylenediamine, 2,4- or 2,6-toluylenediamine, and 2,2-bis(4,4'-diaminophenyl)propane). Examples of the aromatic aliphatic diamine include C7 to C20 aromatic aliphatic diamines (for example, xylylenediamine, bis(aminoethyl)benzene, bis(aminopropyl)benzene, and bis(aminobutyl)benzene).

[0012] Examples of the dicarboxylic acid (a104) include C2-40 dicarboxylic acids, such as aliphatic dicarboxylic acids, aromatic ring-containing dicarboxylic acids, alicyclic dicarboxylic acids, derivatives of these dicarboxylic acids (e.g., acid anhydrides, lower (C1-4) alkyl esters, and dicarboxylic acid salts (e.g., alkali metal salts (e.g., lithium salts, sodium salts, and potassium salts))), and mixtures of two or more of these.

[0013] Examples of aliphatic dicarboxylic acids include C2 to C40 (preferably C4 to C20, and more preferably C6 to C12 from the viewpoints of mechanical strength, antibacterial properties, and antiviral properties) aliphatic dicarboxylic acids (e.g., succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, maleic acid, fumaric acid, and itaconic acid). Examples of aromatic ring-containing dicarboxylic acids include C8 to C40 (preferably C8 to C16, and more preferably C8 to C14 from the viewpoints of mechanical strength and antibacterial and antiviral properties) aromatic ring-containing dicarboxylic acids (e.g., orthophthalic acid, isophthalic acid, terephthalic acid, 2,6- or 2,7-naphthalenedicarboxylic acid, diphenyl-4,4'-dicarboxylic acid, diphenoxyethanedicarboxylic acid, tolylenedicarboxylic acid, xylylenedicarboxylic acid, and 5-sulfoisophthalic acid alkali metal (same as above) salts). Examples of the alicyclic dicarboxylic acid include C5 to C40 (preferably C6 to C18, and more preferably C8 to C14 from the viewpoints of mechanical strength, antibacterial properties, and antiviral properties) alicyclic dicarboxylic acids (e.g., cyclopropanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, cyclohexenedicarboxylic acid, dicyclohexyl-4,4'-dicarboxylic acid, and camphoric acid).

[0014] Of the above amide-forming monomers (a10), ε-caprolactam and 12-aminododecanoic acid are preferred from the viewpoints of mechanical strength, antibacterial properties, and antiviral properties. It is also preferred to combine adipic acid and hexamethylenediamine to form the amide-forming monomer (a10).

[0015] The polyamide (a1) can be produced by ring-opening polymerization or polycondensation of the amide-forming monomer (a10) in the presence of a molecular weight modifier. The molecular weight modifier may be a diamine or a dicarboxylic acid. The diamine and dicarboxylic acid may be one or more of the compounds described above as the diamine (a103) (C2-40, preferably C4-20) and the dicarboxylic acid (a104) (C2-40, preferably C4-20), respectively.

[0016] The amount of the molecular weight modifier used is preferably 2 to 80% by weight, more preferably 4 to 75% by weight, based on the total weight of the amide-forming monomer (a10) and the molecular weight modifier, from the viewpoints of mechanical strength, antibacterial properties, and antiviral properties.

[0017] The number average molecular weight (hereinafter abbreviated as Mn, measured by gel permeation chromatography (GPC)) of the polyamide (a1) is preferably 200 to 5,000, more preferably 500 to 4,000, and particularly preferably 800 to 3,000, from the viewpoints of mechanical strength, antibacterial properties, and antiviral properties.

[0018] The number average molecular weight (Mn) and weight average molecular weight (Mw) of the polymer in the present invention can be measured using gel permeation chromatography (GPC) under the following conditions. Equipment (example): "HLC-8120" [manufactured by Tosoh Corporation] Column (example): "TSKgelGMHXL" [manufactured by Tosoh Corporation] (2 columns) "TSKgel Multipore HXL-M" [manufactured by Tosoh Corporation] (1 tube) Sample solution: 0.3% by weight orthodichlorobenzene solution ·Solution injection volume: 100μl ·Flow rate: 1ml / min ·Measurement temperature: 135℃ Detector: Refractive index detector Reference material: 12 standard polystyrenes (TSKstandardPOLYSTYRENE) (molecular weights: 500, 1,050, 2,800, 5,970, 9,100, 18,100, 37,900, 96,400, 190,000, 355,000, 1,090,000, 2,890,000) [manufactured by Tosoh Corporation]

[0019] <Polyolefin (a2)> The polyolefin (a2) in the present invention is preferably a polyolefin having a reactive group. Examples of the polyolefin (a2) include a polyolefin (a21) having reactive groups at both ends and a polyolefin (a22) having a reactive group at one end. The reactive group refers to a carboxyl group, a carboxylic anhydride group, a hydroxyl group, an amino group, and an isocyanate group.

[0020] <Polyolefin (a21) having reactive groups at both ends> Examples of (a21) include polyolefins (a21-1) having carboxyl groups or carboxylic anhydride groups at both polymer terminals, polyolefins (a21-2) having hydroxyl groups at both polymer terminals, polyolefins (a21-3) having amino groups at both polymer terminals, and polyolefins (a21-4) having isocyanate groups at both polymer terminals. Among these, (a21-1) is preferred from the viewpoints of ease of modification and heat resistance during molding. In the present invention, the term "terminal" refers to the terminal end where the repeating structure of the monomer units constituting the polymer is interrupted, and "both terminals" refers to both terminals of the main chain of the polymer.

[0021] (a21) can be obtained, for example, by introducing a carboxyl group, a carboxylic anhydride group, a hydroxyl group, an amino group, or an isocyanate group into both ends of a polyolefin (a21-0) whose main component is a polyolefin whose both ends can be modified. The term "main component" means that the weight of the polyolefin capable of being modified at both ends accounts for 50% by weight or more of the weight of the entire polyolefin. However, even if the weight of the polyolefin that can be modified at both ends is less than 50% by weight of the total weight of the polyolefin, if the sum of the weight of the polyolefin that can be modified at both ends and the weight of the polyolefin that can be modified at one end, which will be described later, is 50% by weight or more of the total weight of the polyolefin, and the weight of the polyolefin that can be modified at both ends is equal to or greater than the weight of the polyolefin that can be modified at one end, then it is considered to be (a21-0).

[0022] (a21-0) includes polyolefins obtained by (co)polymerizing one or a mixture of two or more olefins having 2 to 30 carbon atoms (preferably 2 to 12, more preferably 2 to 10), containing 30 mol% or more of structural units derived from propylene in the polyolefin, and degraded polyolefins {those obtained by mechanically, thermally, or chemically degrading polyolefins having a high molecular weight [preferably a number average molecular weight (hereinafter abbreviated as Mn) of 10,000 to 150,000]}. Note that (co)polymerization means polymerization or copolymerization.

[0023] Among these, degraded polyolefins are preferred from the viewpoints of ease of modification when introducing a carboxyl group, a carboxylic anhydride group, a hydroxyl group, an amino group, or an isocyanate group, and ease of availability, and thermally degraded polyolefins are even more preferred. Thermal degradation, as described below, easily produces low-molecular-weight polyolefins having 1 to 2 terminal double bonds per molecule, and these low-molecular-weight polyolefins can be easily modified by introducing a carboxyl group, a carboxylic anhydride group, a hydroxyl group, an amino group, an isocyanate group, or the like.

[0024] Examples of thermally degraded polyolefins include those obtained by heating high molecular weight polyolefins in an inert gas (at 300 to 450°C for 0.5 to 10 hours, for example, those obtained by the method described in JP-A-3-62804), and those thermally degraded by heating in air.

[0025] Examples of high-molecular-weight polyolefins used in thermal degradation include (co)polymers of one or more olefins having 2 to 30 carbon atoms (preferably 2 to 12, more preferably 2 to 10 carbon atoms) [Mn is preferably 10,000 to 150,000, more preferably 15,000 to 70,000; melt flow rate (hereinafter abbreviated as MFR, in g / 10 min) is preferably 0.5 to 150, more preferably 1 to 100], and include those containing 30 mol% or more of propylene-derived structural units in the polyolefin. Here, MFR is a numerical value that represents the melt viscosity of a resin; a higher value indicates a lower melt viscosity. MFR is measured according to the method specified in JIS K7210-1 (2014). For example, in the case of polypropylene, it is measured at 230°C under a load of 2.16 kgf. Examples of the olefin having 2 to 30 carbon atoms include α-olefins having 2 to 30 carbon atoms and dienes having 4 to 30 carbon atoms.

[0026] Examples of the α-olefin having 2 to 30 carbon atoms include ethylene, propylene, 1-butene, 4-methyl-1-pentene, 1-pentene, 1-octene, 1-decene, 1-dodecene, 1-icosene, and 1-tetracosene. Examples of dienes having 4 to 30 carbon atoms include butadiene, isoprene, cyclopentadiene, and 1,11-dodecadiene. Among the olefins having 2 to 30 carbon atoms, from the viewpoint of molecular weight control, preferred are α-olefins having 2 to 12 carbon atoms, butadiene, isoprene, and mixtures thereof, more preferred are α-olefins having 2 to 10 carbon atoms, butadiene, and mixtures thereof, and particularly preferred are α-olefins having 2 to 3 carbon atoms, such as ethylene and propylene, and mixtures thereof.

[0027] <Polyolefin (a22) having a reactive group at one end> Examples of (a22) include polyolefins (a22-1) having a carboxyl group or a carboxylic anhydride group at one end of the polymer, polyolefins (a22-2) having a hydroxyl group at one end of the polymer, polyolefins (a22-3) having an amino group at one end of the polymer, polyolefins (a22-4) having an isocyanate group at one end of the polymer, and polyolefins (a22-5) having both a carboxyl group and a hydroxyl group at one end of the polymer. Among these, (a22-1) is preferred from the viewpoints of ease of modification and heat resistance during molding. The term "one end" means either one end of the main chain of the polymer.

[0028] (a22) can be obtained, for example, by introducing a carboxyl group, a carboxylic anhydride group, a hydroxyl group, an amino group, or an isocyanate group into polyolefin (a22-0) mainly composed of a polyolefin whose one end can be modified. The term "main component" means that the weight of the polyolefin capable of being modified at one end accounts for 50% by weight or more of the weight of the entire polyolefin. However, even if the weight of the polyolefin capable of being modified at one end is less than 50% by weight of the total weight of the polyolefin, if the sum of the weight of the polyolefin capable of being modified at one end and the weight of the polyolefin capable of being modified at both ends is 50% by weight or more of the total weight of the polyolefin, and the weight of the polyolefin capable of being modified at one end is greater than the weight of the polyolefin capable of being modified at both ends, then the polyolefin is considered to be (a22-0).

[0029] (a22-0) can be obtained in the same manner as (a21-0).

[0030] (a21-0) and (a22-0) are generally obtained as a mixture thereof, and the mixture may be used as is or after purification and separation. Of these, the mixture is preferred from the viewpoint of production costs, etc.

[0031] Below, we will explain (a21-1) to (a21-4) which have a carboxyl group, a carboxylic acid anhydride group, a hydroxyl group, an amino group, or an isocyanate group at both ends of (a21-0), but (a22-1) to (a22-4) which have these groups at one end of (a22-0) can be obtained in the same manner as (a21-1) to (a21-4) by replacing (a21-0) with (a22-0). The preferred examples of (a21) and (a22) are also the same.

[0032] Examples of (a21-1) that can be used include polyolefins (a21-1-1) having a structure in which the terminals of (a21-0) are modified with an α,β-unsaturated carboxylic acid (anhydride), polyolefins (a21-1-2) having a structure in which (a21-1-1) is secondarily modified with a lactam or an aminocarboxylic acid, polyolefins (a21-1-3) having a structure in which (a21-0) is modified by oxidation or hydroformylation, polyolefins (a21-1-4) having a structure in which (a21-1-3) is secondarily modified with a lactam or an aminocarboxylic acid, and mixtures of two or more of these. The α,β-unsaturated carboxylic acid (anhydride) means an α,β-unsaturated carboxylic acid or an anhydride thereof.

[0033] (a21-1-1) can be obtained by modifying (a21-0) with an α,β-unsaturated carboxylic acid (anhydride). The α,β-unsaturated carboxylic acid (anhydride) used for modification includes monocarboxylic acids, dicarboxylic acids, and anhydrides of mono- or dicarboxylic acids, and specific examples thereof include (meth)acrylic acid, maleic acid (anhydride), fumaric acid, itaconic acid (anhydride), and citraconic acid (anhydride). Among these, from the viewpoint of ease of modification, anhydrides of mono- or dicarboxylic acids and dicarboxylic acids are preferred, maleic acid (anhydride) and fumaric acid are more preferred, and maleic acid (anhydride) is particularly preferred. Incidentally, (meth)acrylic acid means acrylic acid or methacrylic acid.

[0034] (a21-1-2) can be obtained by secondarily modifying (a21-1-1) with the lactam or aminocarboxylic acid.

[0035] (a21-1-3) can be obtained by oxidizing (a21-0) with oxygen and / or ozone (oxidation method), or by introducing a carboxyl group by hydroformylation using the oxo method. Introduction of a carboxyl group by oxidation can be carried out by known methods, for example, the method described in U.S. Patent No. 3,692,877. Introduction of a carboxyl group by hydroformylation can be carried out by various methods including known methods, for example, the method described in Macromolecules, Vol. 31, p. 5943. (a21-1-4) can be obtained by secondarily modifying (a21-1-3) with a lactam or aminocarboxylic acid.

[0036] The acid value of (a21-1) is preferably 4 to 100 mgKOH / g, more preferably 4 to 50 mgKOH / g, and particularly preferably 5 to 30 mgKOH / g, from the viewpoint of reactivity with the hydrophilic polymer (b).

[0037] As (a21-2), polyolefins having hydroxyl groups obtained by modifying (a21-1) with amines having hydroxyl groups, and mixtures of two or more of these can be used. Examples of amines having a hydroxyl group that can be used for modification include amines having a hydroxyl group and having 2 to 10 carbon atoms, such as 2-aminoethanol, 3-aminopropanol, 1-amino-2-propanol, 4-aminobutanol, 5-aminopentanol, 6-aminohexanol, and 3-aminomethyl-3,5,5-trimethylcyclohexanol.

[0038] From the viewpoint of reactivity with the hydrophilic polymer (b), the hydroxyl value of (a21-2) is preferably 4 to 100 mgKOH / g, more preferably 4 to 50 mgKOH / g, and particularly preferably 5 to 30 mgKOH / g.

[0039] As (a21-3), polyolefins having amino groups obtained by modifying (a21-1) with diamines, and mixtures of two or more of these can be used. As the diamine, diamines having 2 to 12 carbon atoms can be used, and specific examples thereof include ethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, and decamethylenediamine. Among these, from the viewpoint of ease of modification, diamines having 2 to 8 carbon atoms (ethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, etc.) are preferred, ethylenediamine and hexamethylenediamine are more preferred, and ethylenediamine is particularly preferred.

[0040] The amine value of (a21-3) is preferably 4 to 100 mgKOH / g, more preferably 4 to 50 mgKOH / g, and particularly preferably 5 to 30 mgKOH / g, from the viewpoint of reactivity with the hydrophilic polymer (b).

[0041] Examples of (a21-4) include polyolefins having an isocyanate group obtained by modifying (a21-2) with poly(2 to 3 or more) isocyanate, and mixtures of two or more of these. Examples of polyisocyanates include aromatic polyisocyanates having 6 to 20 carbon atoms (excluding carbon atoms in isocyanate groups; the same applies below), aliphatic polyisocyanates having 2 to 18 carbon atoms, alicyclic polyisocyanates having 4 to 15 carbon atoms, aromatic aliphatic polyisocyanates having 8 to 15 carbon atoms, modified products of these polyisocyanates, and mixtures of two or more of these.

[0042] As (a22-5), a polyolefin (a22-5-1) having a structure in which one end of (a22-0) is modified with an α,β-unsaturated carboxylic acid anhydride and then secondarily modified with a diolamine can be used. An example of the diolamine used for the secondary modification is diethanolamine.

[0043] In terms of mechanical strength, antibacterial properties, and antiviral properties, Mn in (a21) and (a22) is preferably 1,000 to 25,000, more preferably 1,500 to 12,000, and particularly preferably 2,000 to 7,000.

[0044] <Polyester (a3)> The polyester (a3) ​​in the present invention is, for example, a polymer having a diol (a31) and a dicarboxylic acid (a32) as constituent monomers.

[0045] Examples of the diol (a31) include an aliphatic diol (a311) and an aromatic group-containing diol (a312). Examples of the dicarboxylic acid (a32) include aliphatic dicarboxylic acids (a321) and aromatic dicarboxylic acids (a322). The diol (a31) may be one type alone or a mixture of two or more types.

[0046] Examples of the aliphatic diol (a311) include 1,2-ethanediol (ethylene glycol), 1,2-propanediol (propylene glycol), 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 2-methyl-1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 2,2-dimethyl-1,3-propanediol (neopentyl glycol), 2,2-diethyl-1,3-propanediol (3,3-dimethylolpentane), 2-n-butyl-2-ethyl-1,3propanediol (3,3-dimethylolheptane), Examples of suitable diols include 3-methyl-1,5-pentanediol, 1,6-hexanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol, 2-methyl-1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-octadecanediol, 1,4-cyclohexanedimethanol, hydrogenated bisphenol A, 1,2-, 1,3-, or 1,4-cyclohexanediol, cyclododecanediol, dimer diol, hydrogenated dimer diol, diethylene glycol, dipropylene glycol, and triethylene glycol.

[0047] Examples of the aromatic group-containing diol (a312) include bisphenol A, 1,2-hydroxybenzene, 1,3-hydroxybenzene, 1,4-hydroxybenzene, and 1,4-benzenedimethanol.

[0048] Examples of the aliphatic dicarboxylic acid (a321) include those having 2 to 20 (preferably 4 to 16) carbon atoms, such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, 1,10-decanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, dimer acid, maleic acid, and fumaric acid. The alkyl esters and acid halides mentioned above may also be used as (a321).

[0049] Examples of aromatic dicarboxylic acids (a322) include those having 8 to 20 carbon atoms, such as terephthalic acid, isophthalic acid, phthalic acid, phenylmalonic acid, homophthalic acid, phenylsuccinic acid, β-phenylglutaric acid, α-phenyladipic acid, β-phenyladipic acid, biphenyl-2,2'-dicarboxylic acid, biphenyl-4,4'-dicarboxylic acid, and naphthalenedicarboxylic acid. The alkyl esters and acid halides mentioned above may also be used as (a322).

[0050] The number average molecular weight [hereinafter abbreviated as Mn, measured by gel permeation chromatography (GPC)] of the polyester (a3) ​​is preferably 800 to 8,000, more preferably 1,000 to 6,000, and particularly preferably 2,000 to 4,000, from the viewpoints of mechanical strength, antibacterial properties, and antiviral properties.

[0051] <Hydrophilic polymer (b)> Examples of the hydrophilic polymer (b) in the present invention include the hydrophilic polymers described in Japanese Patent No. 3488163, specifically polyether (b1), polyether-containing hydrophilic polymer (b2), etc. From the viewpoints of mechanical strength, antibacterial properties, and antiviral properties, polyether (b1) is preferred. The hydrophilic polymer (b) in the present invention is preferably 1×10 11 It is a polymer with a volume resistivity of Ω·cm or less.

[0052] Examples of the polyether (b1) include polyether diols (b1-1), polyether diamines (b1-2), and modified products thereof (b1-3). Examples of the polyether diol (b1-1) include those obtained by subjecting the diol (b0) to an addition reaction with an alkylene oxide (hereinafter abbreviated as AO), and specifically include those represented by the general formula (1).

[0053] H-(OR 1 ) a -OE 1-O-(R 2 O) b -H (1) E in general formula (1) 1 is the residue obtained by removing all hydroxyl groups from diol (b0). R in general formula (1) 1 and R 2 are each independently an alkylene group having 2 to 4 carbon atoms, an alkylene group having 5 to 12 carbon atoms, a styrene group, or a chloromethyl group. Examples of the alkylene group having 2 to 4 carbon atoms include an ethylene group, a 1,2- or 1,3-propylene group, and a 1,2-, 1,3-, 1,4-, or 2,3-butylene group. In the general formula (1), a and b are each independently selected from the group consisting of (OR 1 ) and (R 2 O) are the average number of moles added, and each independently is 1 to 300, preferably 2 to 250, and more preferably 10 to 100. R in the case where a and b are each 2 or more in general formula (1) 1 , R 2 may be the same or different, (OR 1 ) a , (R 2 O) b The moieties may be randomly or block bonded.

[0054] Examples of the diol (b0) include aliphatic dihydric alcohols having 2 to 12 carbon atoms, alicyclic dihydric alcohols having 5 to 12 carbon atoms, aromatic dihydric alcohols having 6 to 18 carbon atoms, and tertiary amino group-containing diols.

[0055] Examples of the aliphatic dihydric alcohol having 2 to 12 carbon atoms include ethylene glycol (hereinafter abbreviated as EG), 1,2-propylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, and 1,12-dodecanediol. Examples of the alicyclic dihydric alcohol having 5 to 12 carbon atoms include 1,4-di(hydroxymethyl)cyclohexane and 1,5-di(hydroxymethyl)cycloheptane. Examples of aromatic dihydric alcohols having 6 to 18 carbon atoms include monocyclic aromatic dihydric alcohols (xylylenediol, hydroquinone, catechol, resorcinol, urushiol, etc.) and polycyclic aromatic dihydric alcohols (bisphenol A, bisphenol F, bisphenol S, 4,4'-dihydroxydiphenyl-2,2-butane, dihydroxybiphenyl, dihydroxynaphthalene, binaphthol, etc.).

[0056] Examples of tertiary amino group-containing diols include bishydroxyalkylated products of aliphatic or alicyclic primary amines having 1 to 12 carbon atoms (such as methylamine, ethylamine, cyclopropylamine, 1-propylamine, 2-propylamine, pentylamine, isopentylamine, cyclopentylamine, hexylamine, cyclohexylamine, heptylamine, nonylamine, decylamine, undecylamine, and dodecylamine), and bishydroxyalkylated products of aromatic primary amines having 6 to 12 carbon atoms (such as aniline and benzylamine). Among these, from the viewpoint of reactivity with bishydroxyalkylated products, preferred as diol (b0) are aliphatic dihydric alcohols having 2 to 12 carbon atoms and aromatic dihydric alcohols having 6 to 18 carbon atoms, and more preferred are EG and bisphenol A.

[0057] The polyether diol (b1-1) can be produced by subjecting the diol (b0) to an addition reaction with AO. As the AO, AOs having 2 to 4 carbon atoms [ethylene oxide (hereinafter abbreviated as EO), 1,2- or 1,3-propylene oxide, 1,2-, 1,3-, 1,4- or 2,3-butylene oxide, and combinations of two or more of these are used, but if necessary, other AOs [α-olefin oxides having 5 to 12 carbon atoms, styrene oxide, epihalohydrins (epichlorohydrin, etc.)] can also be used in combination in a small proportion (30% by weight or less based on the total weight of the AO). When two or more AOs are used in combination, the bonding form may be either random bonding or block bonding. Preferred as AO is EO alone or a combination of EO and other AOs.

[0058] The addition reaction of AO can be carried out by a known method, for example, in the presence of an alkali catalyst at a temperature of 100 to 200°C. (OR 1 ) a and (R 2 O) b The content is preferably 5 to 99.8% by weight, more preferably 8 to 99.6% by weight, and particularly preferably 10 to 98% by weight. (OR 1 ) a and (R 2 O) b The content of oxyethylene groups based on the weight of the copolymer is preferably 5 to 100% by weight, more preferably 10 to 100% by weight, particularly preferably 50 to 100% by weight, and most preferably 60 to 100% by weight. As the polyether diol (b1-1), an EO adduct of bisphenol A and polyethylene glycol are preferred.

[0059] The polyetherdiamine (b1-2) may be one represented by the general formula (2). H2N-R 3 -(OR 4 ) c -OE 2 -O-(R 5 O) d -R 6 -NH2(2)

[0060] E in general formula (2) 2 is the residue obtained by removing all hydroxyl groups from diol (b0). Examples of the diol (b0) include the same ones as those exemplified for the polyether diol (b1-1) above, and the preferred ranges are also the same. R in general formula (2) 3 , R 4 , R 5 and R 6are each independently an alkylene group having 2 to 4 carbon atoms, an alkylene group having 5 to 12 carbon atoms, a styrene group, or a chloromethyl group. The alkylene group having 2 to 4 carbon atoms is 1 and R 2 Examples of the above-mentioned examples include the same as those given above. In the general formula (2), c and d are each independently selected from the group consisting of (OR 4 ) and (R 5 O) are the average number of moles added, and each independently is 1 to 300, preferably 2 to 250, and more preferably 10 to 100. R in the case where c and d in the general formula (2) are each 2 or more 4 , R 5 may be the same or different, (OR 4 ) c , (R 5 O) d The moieties may be randomly or block bonded.

[0061] Polyetherdiamine (b1-2) can be obtained by converting all hydroxyl groups of polyetherdiol (b1-1) to alkylamino groups, for example, by reacting polyetherdiol (b1-1) with acrylonitrile and hydrogenating the resulting cyanoethylated product.

[0062] Examples of the modified product (b1-3) include aminocarboxylic acid modified products (terminal amino group), isocyanate modified products (terminal isocyanate group), and epoxy modified products (terminal epoxy group) of the polyether diol (b1-1) or polyether diamine (b1-2). The aminocarboxylic acid modified product can be obtained by reacting the polyetherdiol (b1-1) or the polyetherdiamine (b1-2) with an aminocarboxylic acid or a lactam. The isocyanate-modified product can be obtained by reacting the polyetherdiol (b1-1) or polyetherdiamine (b1-2) with a polyisocyanate, or by reacting the polyetherdiamine (b1-2) with phosgene. The epoxy-modified product can be obtained by reacting a polyetherdiol (b1-1) or a polyetherdiamine (b1-2) with a diepoxide (an epoxy resin such as a diglycidyl ether, a diglycidyl ester, or an alicyclic diepoxide: epoxy equivalent of 85 to 600), or by reacting a polyetherdiol (b1-1) with an epihalohydrin (epichlorohydrin, etc.).

[0063] From the viewpoints of heat resistance and reactivity with the hydrophobic polymer (a), the Mn of the hydrophilic polymer (b) is preferably 150 to 20,000, more preferably 300 to 18,000, particularly preferably 1,000 to 15,000, and most preferably 1,200 to 8,000.

[0064] <Block polymer (A)> The block polymer (A) in the present invention has a block of the hydrophobic polymer (a) and a block of the hydrophilic polymer (b) as constituent units. The hydrophobic polymer (a) and the hydrophilic polymer (b) constituting the block polymer (A) may each be one type or two or more types.

[0065] The weight ratio [(a) / (b)] of the block of hydrophobic polymer (a) to the block of hydrophilic polymer (b) constituting the block polymer (A) is preferably 10 / 90 to 80 / 20, more preferably 20 / 80 to 75 / 25, from the viewpoints of mechanical strength, antibacterial property, antiviral property, and their durability.

[0066] The structure in which a block of hydrophobic polymer (a) and a block of hydrophilic polymer (b) constituting the block polymer (A) are bonded includes (a)-(b) type, (a)-(b)-(a) type, (b)-(a)-(b) type, and [(a)-(b)]n type (n represents the average number of repetitions). From the viewpoint of electrical conductivity, the structure of the block polymer (A) is preferably an [(a)-(b)]n type in which hydrophobic polymers (a) and hydrophilic polymers (b) are repeatedly and alternately bonded. In the [(a)-(b)]n structure, n is preferably 2 to 50, more preferably 2.3 to 30, particularly preferably 2.7 to 20, and most preferably 3 to 10, from the viewpoints of mechanical strength, antibacterial properties, and antiviral properties. n is the ratio of Mn and Mn of the block polymer (A) to the total number of blocks. 1 It can be determined by H-NMR analysis.

[0067] From the viewpoint of the mechanical strength, antibacterial properties and antiviral properties of the molded article described below, Mn of the block polymer (A) is preferably 2,000 to 100,000, more preferably 5,000 to 60,000, and particularly preferably 10,000 to 40,000.

[0068] When the block polymer (A) has a structure in which the block of the hydrophobic polymer (a) and the block of the hydrophilic polymer (b) are bonded via an ester bond, an amide bond, an ether bond, or an imide bond, it can be produced by the following method. Of the above bonds, from an industrial point of view, ester bonds and amide bonds are preferred.

[0069] One example is a method in which a hydrophobic polymer (a) and a hydrophilic polymer (b) are charged into a reaction vessel and reacted under stirring at a reaction temperature of 100 to 250°C and a pressure of 0.003 to 0.1 MPa for 1 to 50 hours while removing water generated in the amidation, esterification, or imidization reaction (hereinafter referred to as generated water) from the reaction system. The weight ratio of the hydrophobic polymer (a) to the hydrophilic polymer (b) used in the reaction [hydrophobic polymer (a) / hydrophilic polymer (b)] is 10 / 90 to 80 / 20, more preferably 20 / 80 to 75 / 25, from the viewpoints of mechanical strength, antibacterial and antiviral properties, and their durability.

[0070] In the case of an esterification reaction, it is preferable to use 0.05 to 0.5 wt. % of a catalyst based on the total weight of the hydrophobic polymer (a) and the hydrophilic polymer (b) to promote the reaction. Examples of catalysts include inorganic acids (such as sulfuric acid and hydrochloric acid), organic sulfonic acids (such as methanesulfonic acid, paratoluenesulfonic acid, xylenesulfonic acid, and naphthalenesulfonic acid), antimony catalysts (such as antimony trioxide), tin catalysts (such as monobutyltin oxide and dibutyltin oxide), titanium catalysts (such as tetrabutyl titanate, bistriethanolamine titanate, and potassium oxalate titanate), zirconium catalysts (such as tetrabutyl zirconate and zirconium oxyacetate), and zinc catalysts (such as zinc acetate). When a catalyst is used, it can be neutralized after the esterification reaction is complete, if necessary, and then removed and purified by treatment with an adsorbent.

[0071] The generated water can be removed from the reaction system by the following methods. (1) A method in which an organic solvent that is not miscible with water (e.g., toluene, xylene, cyclohexane, etc.) is used, and the organic solvent and the generated water are azeotropically distilled under reflux, and only the generated water is removed from the reaction system. (2) A method in which a carrier gas (such as air, nitrogen, helium, argon, or carbon dioxide) is blown into the reaction system and the generated water is removed from the reaction system together with the carrier gas. (3) A method in which the reaction system is decompressed to remove the generated water from the reaction system.

[0072] <Sulfonate (S)> Examples of the sulfonate (S) in the present invention include alkyl (alkyl having 6 to 18 carbon atoms) benzenesulfonate, alkyl (alkyl having 6 to 18 carbon atoms) sulfonate, and perfluoroalkane (alkane having 1 to 3 carbon atoms) sulfonate.

[0073] Among the above sulfonates (S), alkyl (alkyl having 6 to 18 carbon atoms) benzenesulfonates and perfluoroalkane (alkane having 1 to 3 carbon atoms) sulfonates are preferred from the viewpoint of antibacterial and antiviral properties and their durability.

[0074] Examples of the anion constituting the alkyl (alkyl having 6 to 18 carbon atoms, preferably 10 to 14 carbon atoms) benzenesulfonate include a hexylbenzenesulfonate anion, a decylbenzenesulfonate anion, an undecylbenzenesulfonate anion, a dodecylbenzenesulfonate anion, a tridecylbenzenesulfonate anion, a tetradecylbenzenesulfonate anion, and an octadecylbenzenesulfonate anion. Examples of the anion constituting the alkyl (alkyl having 6 to 18 carbon atoms, preferably 10 to 14 carbon atoms) sulfonate include a hexyl sulfonate anion, a decyl sulfonate anion, an undecyl sulfonate anion, a dodecyl sulfonate anion, a tridecyl sulfonate anion, a tetradecyl sulfonate anion, and an octadecyl sulfonate anion. Examples of anions constituting the perfluoroalkane (alkane having 1 to 3 carbon atoms) sulfonate include trifluoromethanesulfonate anion, pentafluoroethanesulfonate anion, and heptafluoropropanesulfonate anion. Of the anions constituting the sulfonate (S), alkyl (alkyl having 6 to 18 carbon atoms) benzenesulfonate anion and perfluoroalkane (alkane having 1 to 3 carbon atoms) sulfonate anion are preferred.

[0075] Of the anions constituting the sulfonate (S), alkyl (alkyl having 6 to 18 carbon atoms) benzenesulfonate anion and perfluoroalkane (alkane having 1 to 3 carbon atoms) sulfonate anion are preferred.

[0076] Examples of the cation that constitutes the sulfonate (S) include alkali metal (for example, lithium, sodium, potassium) cations and imidazolium cations.

[0077] The imidazolium cations include C5 to C15 imidazolium cations, such as 1,3-dimethylimidazolium, 1,3-diethylimidazolium, 1-ethyl-3-methylimidazolium, 1-butyl-3-methylimidazolium, 1,2,3-trimethylimidazolium, 1,2,3,4-tetramethylimidazolium, 1-ethyl-2,3-dimethylimidazolium, and 1,3-dimethylimidazolium. Methyl-2-ethylimidazolium, 1,2-dimethyl-3-ethyl-imidazolium, 1,2,3-triethylimidazolium, 1,2,3,4-tetraethylimidazolium, 1,3-dimethyl-2-phenylimidazolium, 1,3-dimethyl-2-benzylimidazolium, 1-benzyl-2,3-dimethyl-imidazolium, 4-cyano-1,2,3-trimethylimidazolium, 3-cyano Examples of such compounds include anomethyl-1,2-dimethylimidazolium, 2-cyanomethyl-1,3-dimethyl-imidazolium, 4-acetyl-1,2,3-trimethylimidazolium, 3-acetylmethyl-1,2-dimethylimidazolium, 4-methylcarboxymethyl-1,2,3-trimethylimidazolium, 3-methylcarboxymethyl-1,2-dimethylimidazolium, 4-methoxy-1,2,3-trimethylimidazolium, 3-methoxymethyl-1,2-dimethylimidazolium, 4-formyl-1,2,3-trimethylimidazolium, 3-formylmethyl-1,2-dimethylimidazolium, 3-hydroxyethyl-1,2-dimethylimidazolium, 4-hydroxymethyl-1,2,3-trimethylimidazolium, and 2-hydroxyethyl-1,3-dimethylimidazolium.

[0078] Of the cations constituting the salt (S), from the viewpoint of antibacterial and antiviral properties, alkali metal ions and imidazolium are preferred, lithium, sodium, 1-alkyl (alkyl having 1 to 3 carbon atoms) 3-alkyl (alkyl having 1 to 3 carbon atoms) imidazolium are more preferred, and 1-ethyl-3-methylimidazolium is particularly preferred, as well as a combination of lithium and 1-ethyl-3-methylimidazolium, and a combination of sodium and 1-ethyl-3-methylimidazolium.

[0079] Examples of the salt (S) include salts composed of the above anions and cations. Among the sulfonates (S), from the viewpoints of antibacterial and antiviral properties and their durability, preferred are imidazolium alkyl (alkyl having 6 to 18 carbon atoms)benzenesulfonates, alkali metal salts of perfluoroalkane (alkane having 1 to 3 carbon atoms) sulfonates, and combinations thereof, and more preferred are imidazolium dodecylbenzenesulfonates, alkali metal salts of trifluoromethanesulfonates, and combinations thereof.

[0080] <Antibacterial and antiviral agent (Z)> The antibacterial and antiviral agent (Z) of the present invention contains the block polymer (A) and the sulfonate (S). The antibacterial and antiviral agent (Z) can be used for various purposes, but is particularly suitable as an antibacterial and antiviral agent for thermoplastic resins. The weight ratio of the block polymer (A) to the sulfonate (S) [(A) / (S)] is preferably 90 / 10 to 99 / 1, more preferably 92 / 8 to 98 / 2, and even more preferably 94 / 6 to 97 / 3.

[0081] The antibacterial and antiviral agent (Z) can be produced, for example, by any one of the following methods (1) and (2). (1) The block polymer (A) and the sulfonate (S) are mixed together. (2) When the polymer of the hydrophobic block (a) and the polymer of the hydrophilic block (b) are reacted by a known method to obtain the block polymer (A), the sulfonate (S) is added before or during the reaction.

[0082] <Resin composition (Y)> The resin composition (Y) of the present invention contains the antibacterial and antiviral agent (Z) and a thermoplastic resin (E) described below. The weight ratio of the antibacterial and antiviral agent (Z) to the thermoplastic resin (E) [(Z) / (E)] is preferably 3 / 97 to 30 / 70, more preferably 5 / 95 to 25 / 75, and particularly preferably 10 / 90 to 20 / 80, from the viewpoints of mechanical strength, antibacterial activity, antiviral activity, and their durability.

[0083] Examples of the thermoplastic resin (E) include polyphenylene ether resin (E1); vinyl resin [polyolefin resin (E2) [e.g., polypropylene, polyethylene, ethylene-vinyl acetate copolymer resin (EVA), ethylene-ethyl acrylate copolymer resin], poly(meth)acrylic resin (E3) [e.g., polymethyl methacrylate], polystyrene resin (E4) [vinyl group-containing aromatic hydrocarbon alone or a copolymer containing vinyl group-containing aromatic hydrocarbon and at least one selected from the group consisting of (meth)acrylic acid ester, (meth)acrylonitrile and butadiene as a constituent unit, such as polystyrene (PS), styrene / acrylonitrile copolymer (AN resin), acrylonitrile / butadiene / styrene copolymer (ABS resin)]. resin), methyl methacrylate / butadiene / styrene copolymer (MBS resin), styrene / methyl methacrylate copolymer (MS resin)], etc.); polyester resin (E5) [for example, polyethylene terephthalate, polybutylene terephthalate, polycyclohexanedimethylene terephthalate, polybutylene adipate, polyethylene adipate]; polyamide resin (E6) [for example, nylon 66, nylon 69, nylon 612, nylon 6, nylon 11, nylon 12, nylon 46, nylon 6 / 66, nylon 6 / 12]; polycarbonate resin (E7) [for example, polycarbonate (PC), polycarbonate / ABS alloy resin]; polyacetal resin (E8), and mixtures of two or more thereof.

[0084] Among these, from the viewpoints of the mechanical strength of the molded article, the antibacterial and antiviral properties, and the durability of these properties, which will be described later, polyolefin resin (E2), polystyrene resin (E4), and polycarbonate resin (E7) are preferred, and polystyrene resin (E4) is more preferred.

[0085] The resin composition (Y) of the present invention may contain, if necessary, a known resin additive (G) in addition to the block polymer (A), sulfonate (S), and thermoplastic resin (E) described above, within a range that does not impair the effects of the present invention. Examples of the resin additive (G) include compatibilizers (such as carboxylic acid-modified polypropylene), flame retardants (such as guanamine), pigments (such as titanium oxide), dyes (such as azo dyes), nucleating agents (such as talc), lubricants (such as carbamara wax), plasticizers (such as dioctyl phthalate), antioxidants (such as triphenyl phosphite), and ultraviolet absorbers [such as 2-(2'-hydroxy-5'-methylphenyl)benzotriazole]. The content of the resin additive (G) varies depending on the application, but is, for example, 45% by weight or less based on the total weight of the antibacterial and antiviral agent (Z) and the thermoplastic resin (E), and from the viewpoint of the effect of the addition, is preferably 0.01 to 30% by weight, and more preferably 0.1 to 10% by weight.

[0086] The resin composition (Y) of the present invention can be obtained by melt-mixing the antibacterial and antiviral agent (Z), the thermoplastic resin (E), and, if necessary, the resin additive (G). As a method for melt mixing, generally, pellet-like or powder-like components are mixed in an appropriate mixer, such as a Henschel mixer, and then melt-mixed in an extruder to form pellets. The order of addition of the components during melt mixing is not particularly limited. For example, (1) A method of melt-mixing the antibacterial and antiviral agent (Z), the thermoplastic resin (E), and, if necessary, the resin additive (G) all at once, (2) A method in which the antibacterial and antiviral agent (Z) and a portion of the thermoplastic resin (E) are melt-mixed in advance to prepare a high-concentration resin composition of the antibacterial and antiviral agent (Z) (masterbatch resin composition), and then the remaining thermoplastic resin (E) and, if necessary, the resin additive (G) are melt-mixed.

[0087] <Molded products> The molded article of the present invention can be obtained by molding the resin composition (Y) using any molding method, such as injection molding, compression molding, calendar molding, slush molding, rotational molding, extrusion molding, blow molding, foam molding, or film molding (casting, tenter molding, inflation molding, etc.).

[0088] The antibacterial and antiviral agent (Z) of the present invention imparts excellent antibacterial activity and its durability to the thermoplastic resin (E), and further imparts excellent antiviral activity and its durability to the thermoplastic resin, and also provides molded articles of the resin composition (Y) with excellent mechanical strength. This allows it to be molded using a variety of molding methods, including injection molding, compression molding, calendar molding, slush molding, rotational molding, extrusion molding, blow molding, foam molding, and film molding (e.g., casting, tenter molding, and inflation molding). Its molded products include housing products (for home appliances, office equipment, game consoles, and office machines), medical materials (masks, gloves, protective clothing, medical device housings, etc.), various cushioning materials, covering materials (packaging films, protective films, etc.), flooring sheets, artificial turf, mats, tape substrates (for semiconductor manufacturing processes, etc.), and various molded products (automotive parts, etc.), and are particularly useful as medical materials. [Example]

[0089] The present invention will be further explained below with reference to examples and comparative examples, but the present invention is not limited thereto. Unless otherwise specified, parts below mean parts by weight.

[0090] <Production Example 1> [Production of polyamide (a-1)] 79.4 parts of ε-caprolactam, 11.5 parts of terephthalic acid, 0.3 parts of an antioxidant ("Irganox 1010", manufactured by BASF Japan Ltd.) and 6 parts of water were placed in a stainless steel pressure-resistant reactor equipped with a stirrer, a thermometer, a heating / cooling device, a nitrogen inlet tube and a pressure reducing device, and after replacing with nitrogen, the mixture was heated to 220°C with stirring in a sealed state and then stirred at the same temperature (pressure: 0.2 to 0.3 MPa) for 4 hours to obtain a polyamide (a-1) having carboxyl groups at both ends. The acid value of (a-1) was 78 and Mn was 1,400.

[0091] <Production Example 2> [Production of polyolefin (a2-1-1α) having carboxyl groups at both ends] A pressure-resistant reactor similar to that used in Production Example 1 was charged with 90 parts of a low-molecular-weight polypropylene obtained by thermal degradation [obtained by thermally degrading polypropylene (MFR: 10 g / 10 min) at 410±0.1°C for 16 minutes under nitrogen aeration (80 mL / min), Mn: 3,400, number of double bonds per 1,000 carbon atoms: 7.0, average number of double bonds per molecule: 1.8, content of both end-modifiable polyolefin: 90 wt %], 10 parts of maleic anhydride, and 30 parts of xylene. The mixture was mixed uniformly, then purged with nitrogen, and the mixture was heated to 200°C under a sealed condition with stirring to melt the mixture, and reacted at that temperature for 10 hours. Next, excess maleic anhydride and xylene were distilled off under reduced pressure (0.013 MPa or less) at 200°C over 3 hours to obtain 95 parts of polyolefin (a2-1-1α) having carboxyl groups at both polymer terminals. The acid value of (a2-1-1α) was 27.5 and Mn was 3,600.

[0092] <Production Example 3> [Production of polyolefin (a2-1-2) obtained by secondary modification of (a2-1-1α)] 88 parts of (a2-1-1α) and 12 parts of 12-aminododecanoic acid were placed in a pressure-resistant reaction vessel similar to that used in Production Example 1, and after uniform mixing, the mixture was heated to 200°C while stirring under a nitrogen gas atmosphere, and reacted at the same temperature under reduced pressure (0.013 MPa or less) for 3 hours, yielding 96 parts of polyolefin (a2-1-2) obtained by secondary modification of (a2-1-1α). The acid value of (a2-1-2) was 24.8 and Mn was 4,000.

[0093] <Production Example 4> [Production of polyester (a-3)] 68.4 parts of dodecane diacid, 31.6 parts of 1,6-hexanediol, and 0.3 parts of antioxidant (Irganox 1010, manufactured by BASF Japan Ltd.) were placed in a stainless steel pressure-resistant reaction vessel equipped with a stirrer, a thermometer, a heating / cooling device, a nitrogen inlet tube, and a pressure reducing device, and the mixture was polymerized at normal pressure for 4 hours while gradually increasing the temperature from 160°C to 210°C, and then at 210°C under reduced pressure for 3 hours to obtain polyester (a-3) having carboxyl groups at both ends. The acid value of (a-3) was 37 and the Mn was 3,000.

[0094] <Production Example 11> [Block polymer (A-1)] 223 parts of polyamide (a-1), 279 parts of an EO adduct of bisphenol A (Mn: 1,800), and 7 parts of zirconium oxyacetate were placed in a reaction vessel equipped with a stirrer, a thermometer, and a heating / cooling device, and the mixture was heated to 240°C with stirring and polymerized at the same temperature for 6 hours under reduced pressure (0.013 MPa or less) to obtain a block polymer (A-1). The Mn of (A-1) was 22,000, and the weight ratio [(a) / (b)] was 44 / 56.

[0095] <Production Example 12> [Block polymer (A-2)] Into a pressure-resistant reaction vessel similar to that in Production Example 11, 60.1 parts of (a2-1-2), 60.1 parts of polyether diol (b1-1α) [PEG (Mn: 3,000, volume resistivity: 1 × 10 × 7 39.9 parts of Ω·cm), 0.3 parts of the antioxidant "Irganox 1010", and 0.5 parts of zirconyl acetate were added, and the temperature was raised to 220°C with stirring. Polymerization was carried out at the same temperature under reduced pressure (0.013 MPa or less) for 3 hours to obtain a viscous block polymer (A-2). The Mn of (A-2) was 30,000, and the weight ratio [(a) / (b)] was 60 / 40.

[0096] <Production Example 13> [Block polymer (A-3)] Into a pressure-resistant reaction vessel similar to that in Production Example 11, 50 parts of (a-3), 10 parts of polyetherdiol (b1-1α) [PEG (Mn: 3,000, volume resistivity: 1 × 10 × 7 50 parts of OH₂·cm), 0.3 parts of the antioxidant "Irganox 1010", and 0.5 parts of zirconyl acetate were added, and the temperature was raised to 220°C while stirring. Polymerization was carried out at the same temperature under reduced pressure (0.013 MPa or less) for 3 hours to obtain a viscous block polymer (A-3). The Mn of (A-3) was 24,000, and the weight ratio [(a) / (b)] was 50 / 50.

[0097] Example 1 A reaction vessel equipped with a stirrer, a thermometer, and a heating / cooling device was charged with 96 parts of the block polymer (A-1) and 4 parts of sodium undecylbenzenesulfonate (S-1), and the mixture was mixed and stirred at 220°C for 1 hour. The mixture was then taken out in the form of strands on a belt and pelletized to obtain an antibacterial and antiviral agent (Z-1).

[0098] <Examples 2 to 14, Comparative Example 1> Each antibacterial and antiviral agent (Z) was obtained in the same manner as in Example 1, except for following the compounding compositions (parts) in Table 1. The results are shown in Table 1. For comparison, silver zeolite ("Zeomic AW10N", manufactured by Sinanen Zeomic Co., Ltd.) was used as an antibacterial and antiviral agent (Comparative Example 1).

[0099] [Table 1]

[0100] <Examples 15 to 31, Comparative Example 2> According to the formulation shown in Table 2, the antibacterial and antiviral agent (Z) and thermoplastic resin (E) were blended for 3 minutes using a Henschel mixer, and then the mixture was melt-kneaded at 230°C using a vented twin-screw extruder at a rotation speed of 100 rpm for a residence time of 3 minutes, to obtain each resin composition (Y). Each of the obtained resin compositions (Y) was molded using an injection molding machine "PS40E5ASE" (manufactured by Nissei Plastic Industrial Co., Ltd.) at a cylinder temperature of 220°C and a mold temperature of 50°C to produce injection-molded articles (100mm x 100mm x 2mm) and injection-molded articles (127mm x 10mm x 4mm), which were evaluated according to the <Evaluation Methods> described below. The results are shown in Table 2.

[0101] <Evaluation method> (1) Antibacterial properties The antibacterial properties of the obtained injection-molded products were evaluated according to JIS Z 2801 (antibacterial processed products - antibacterial test method, antibacterial effect). A 500-fold dilution of normal bouillon medium with sterilized purified water resulted in a bacterial count of 2.5 x 10 5 ~10×1 0 5 0.4 ml of the test bacterial solution, prepared to give a concentration of colony-forming units / ml, was dropped onto a test piece cut into 50 mm x 50 mm x 2 mm from an injection-molded product (100 mm x 100 mm x 2 mm), and the test piece was covered with film and cultured for 24 ± 1 hours at a temperature of 35 ± 1°C and a relative humidity of 90% or higher. The test piece and film were then washed out with 10 ml of SCDLP medium, and the liquid was immediately used to measure the viable bacterial count, determining the viable bacterial count (number of colony-forming units / ml).

[0102] <Evaluation criteria> ☆: 0 ≦ viable bacteria count ≦ 50 ◎: 50 < viable bacteria count ≦ 100 〇: 100 < viable bacteria count ≦ 200 ×: 200 < viable bacteria count

[0103] (2) Durability of antibacterial properties The obtained injection-molded article was washed with water and dried in a circulating air dryer for 3 hours at 80° C. This procedure was repeated a total of three times, and then the antibacterial properties of the injection-molded article were evaluated in the same manner as in the method (1) above.

[0104] <Evaluation criteria> ☆: 0 ≦ viable bacteria count ≦ 50 ◎: 50 < viable bacteria count ≦ 100 〇: 100 < viable bacteria count ≦ 200 ×: 200 < viable bacteria count

[0105] (3) Antiviral The antiviral properties of the resulting injection-molded products were evaluated in accordance with ISO 21702 (Measurement of antiviral activity on plastics and other non-porous surfaces). 1×10 7 ~5×10 7 A 0.4 ml sample of a virus (H3N2) suspension prepared to a concentration of PFU / ml was dropped onto a test piece cut into 50 mm x 50 mm x 2 mm from an injection-molded product (100 mm x 100 mm x 2 mm), and the test piece was covered with film and left to stand at a temperature of 25 ± 1°C and a relative humidity of 90% or higher for 24 ± 1 hours. The test piece and film were then washed with 10 ml of SCDLP medium, and a 10-fold dilution series was prepared. Plaques were measured on 1 cm of the test piece using the plaque measurement method. 2 The viral infectivity per unit area was calculated. Furthermore, a test piece consisting of only the thermoplastic resin (E) was prepared in the same manner as above, and the virus infectivity was determined.

[0106] <Evaluation criteria> Each test specimen was classified as follows depending on how many orders of magnitude the viral infectivity titer determined above was reduced by compared with the corresponding test specimen made of only thermoplastic resin (E). ☆: 4 or more digits ◎: Less than 4 digits, 3 digits or more ○: Less than 3 digits, 2 digits or more ×: Less than 2 digits

[0107] (4) Durable antiviral activity The obtained injection-molded article was washed with water and dried in a circulating air dryer for 3 hours at 80° C. This procedure was repeated a total of three times, and then test specimens were prepared in the same manner as in (3) above, and the virus infectivity was determined.

[0108] <Evaluation criteria> Each test specimen was classified as follows depending on how many orders of magnitude the viral infectivity titer determined in (4) above had decreased compared to the corresponding test specimen made of only thermoplastic resin (E). ☆: 4 or more digits ◎: Less than 4 digits, 3 digits or more ○: Less than 3 digits, 2 digits or more ×: Less than 2 digits

[0109] (5) Mechanical strength (Izod impact value) Measurement was carried out in accordance with ASTM D256 (1984) using Method A. The test specimen was cut out to 63.5 mm x 10 mm x 4 mm from an injection molded product (127 mm x 10 mm x 4 mm) and notched (3.2 mm thick). Similarly, test pieces were also prepared from injection-molded articles made only of the thermoplastic resin (E) and were evaluated.

[0110] <Evaluation criteria> Each test piece was classified as follows depending on what percentage the Izod impact value determined above was relative to the Izod impact value of the corresponding test piece made of only the thermoplastic resin (E). ◎: 80% or more ○: Less than 80%, 70% or more ×: Less than 70%

[0111] [Table 2]

[0112] Thermoplastic resin (E) (E-1): PC / ABS resin [product name: "Sycoloy C6600", manufactured by SABIC Innovative Plastics Japan, LLC] (E-2): Polypropylene resin [product name "SunAllomer PM771M", manufactured by SunAllomer Co., Ltd.] (E-3): Impact-resistant PS resin [product name: HIPS 433, manufactured by PS Japan Co., Ltd.]

[0113] The results in Tables 1 and 2 show that the antibacterial and antiviral agent (Z) of the present invention imparts superior antibacterial and antiviral properties and their durability to thermoplastic resins compared with the comparative agents. Furthermore, the molded articles have excellent mechanical strength. [Industrial Applicability]

[0114] The antibacterial and antiviral agent (Z) of the present invention imparts excellent antibacterial activity and its durability to the thermoplastic resin (E), and further imparts excellent antiviral activity and its durability to the thermoplastic resin, and also provides molded articles of the resin composition (Y) with excellent mechanical strength. This allows it to be molded using a variety of molding methods, including injection molding, compression molding, calendar molding, slush molding, rotational molding, extrusion molding, blow molding, foam molding, and film molding (e.g., casting, tenter molding, and inflation molding). Its molded products include housing products (for home appliances, office equipment, game consoles, and office machines), medical materials (masks, gloves, protective clothing, medical device housings, etc.), various cushioning materials, covering materials (packaging films, protective films, etc.), flooring sheets, artificial turf, mats, tape substrates (for semiconductor manufacturing processes, etc.), and various molded products (automotive parts, etc.), and are particularly useful as medical materials.

Claims

1. 1 x 10 １１ A block of a hydrophobic polymer (a) having a volume resistivity of more than 1×10 １１ An antibacterial and antiviral agent (Z) comprising a block polymer (A) having, as a structural unit, a block of a hydrophilic polymer (b) having a volume resistivity of Ω cm or less, and a sulfonate (S), wherein the hydrophobic polymer (a) is at least one selected from the group consisting of polyamide (a1), polyolefin (a2), and polyester (a3), the hydrophilic polymer (b) is polyether (b1), and the cation constituting the sulfonate (S) is at least one selected from the group consisting of an imidazolium cation and an alkali metal ion.

2. 2. The antibacterial and antiviral agent according to claim 1, wherein the weight ratio [(a) / (b)] of the block (a) to the block (b) constituting the block polymer (A) is 10 / 90 to 80 / 20.

3. The antibacterial and antiviral agent according to claim 1 or 2, wherein the block polymer (A) has a number average molecular weight of 10,000 to 100,000.

4. The antibacterial and antiviral agent according to any one of claims 1 to 3, wherein the anion constituting the sulfonate (S) is at least one selected from the group consisting of an alkyl (alkyl having 6 to 18 carbon atoms) benzenesulfonate anion and a perfluoroalkane (alkane having 1 to 3 carbon atoms) sulfonate anion.

5. The antibacterial and antiviral agent according to any one of claims 1 to 4, wherein the weight ratio of the block polymer (A) to the sulfonate (S) [(A) / (S)] is 90 / 10 to 99 / 1.

6. A resin composition (Y) comprising the antibacterial and antiviral agent (Z) according to any one of claims 1 to 5 and a thermoplastic resin (E).

7. 7. The resin composition according to claim 6, wherein the weight ratio of the antibacterial and antiviral agent (Z) to the thermoplastic resin (E) [(Z) / (E)] is 3 / 97 to 30 / 70.

8. A molded article obtained by molding the resin composition (Y) according to claim 6 or 7.

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