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WO2023013687A1 - Composition d'agent antibactérien/antiviral, structure antibactérienne/antivirale et procédé de production de structure antibactérienne/antivirale - Google Patents

Composition d'agent antibactérien/antiviral, structure antibactérienne/antivirale et procédé de production de structure antibactérienne/antivirale Download PDF

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Publication number
WO2023013687A1
WO2023013687A1 PCT/JP2022/029827 JP2022029827W WO2023013687A1 WO 2023013687 A1 WO2023013687 A1 WO 2023013687A1 JP 2022029827 W JP2022029827 W JP 2022029827W WO 2023013687 A1 WO2023013687 A1 WO 2023013687A1
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WO
WIPO (PCT)
Prior art keywords
meth
acrylate
antibacterial
antiviral
acid
Prior art date
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Ceased
Application number
PCT/JP2022/029827
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English (en)
Japanese (ja)
Inventor
真一 坂下
深雪 梅村
泰士郎 堀口
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Nicca Chemical Co Ltd
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Nicca Chemical Co Ltd
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Filing date
Publication date
Application filed by Nicca Chemical Co Ltd filed Critical Nicca Chemical Co Ltd
Priority to JP2022550183A priority Critical patent/JP7265097B1/ja
Priority to CN202280053983.8A priority patent/CN117794373A/zh
Priority to JP2022166426A priority patent/JP7545455B2/ja
Publication of WO2023013687A1 publication Critical patent/WO2023013687A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/08—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing solids as carriers or diluents
    • A01N25/10—Macromolecular compounds
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
    • A01N57/10—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-oxygen bonds or phosphorus-to-sulfur bonds
    • A01N57/12—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-oxygen bonds or phosphorus-to-sulfur bonds containing acyclic or cycloaliphatic radicals
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
    • A01P1/00—Disinfectants; Antimicrobial compounds or mixtures thereof
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
    • A01P3/00—Fungicides
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2/00—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor
    • A61L2/16—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor using chemical substances
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D201/00—Coating compositions based on unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/63—Additives non-macromolecular organic

Definitions

  • This application discloses an antibacterial/antiviral agent composition, an antibacterial/antiviral structure, and a method for producing the antibacterial/antiviral structure.
  • Patent Document 1 discloses a virus inactivating agent containing sodium dodecyl sulfate as an active ingredient.
  • Patent Document 2 discloses a method of inactivating lipid-enveloped viruses with a nonionic surfactant selected from the group of polysorbates.
  • an antibacterial/antiviral composition comprising at least one of:
  • R 1 , R 2 and R 3 are each independently an alkyl group having 8 to 20 carbon atoms
  • a 1 , A 2 and A 3 are each independently an alkylene group having 2 to 4 carbon atoms
  • x, y and z are each independently an integer of 0-10.
  • R 1 , R 2 and R 3 may have branches.
  • the present application discloses an antibacterial/antiviral structure comprising a base material and the antibacterial/antiviral agent composition of the present disclosure.
  • the present application discloses a method for producing an antibacterial/antiviral structure, which comprises bringing the antibacterial/antiviral agent composition of the present disclosure into contact with a substrate.
  • the antibacterial/antiviral agent composition of the present disclosure has excellent antiviral properties.
  • An antibacterial/antiviral agent composition according to one embodiment comprises a phosphoric acid monoester or a salt thereof represented by the following general formula (1), and a general formula (2) below. Phosphate diester or its salt, and at least one of.
  • R 1 , R 2 and R 3 are each independently an alkyl group having 8 to 20 carbon atoms
  • a 1 , A 2 and A 3 are each independently an alkylene group having 2 to 4 carbon atoms
  • x, y and z are each independently an integer of 0-10.
  • R 1 , R 2 and R 3 are each independently an alkyl group having 8 to 20 carbon atoms. Thus, excellent antiviral properties are exhibited when R 1 , R 2 and R 3 have 8 to 20 carbon atoms.
  • the lower limit of the carbon number is preferably 9 or more, and the upper limit is preferably 18 or less, more preferably 16 or less, and even more preferably 15 or less.
  • R 1 , R 2 and R 3 may each be linear or branched, but particularly when R 1 , R 2 and R 3 are branched, It can easily become better.
  • x, y and z are each independently an integer of 0-10. From the viewpoint of antiviral properties, x, y and z are preferably smaller. Specifically, when x, y and z are each independently an integer of 0 to 8, particularly an integer of 0 to 5, the antiviral properties tend to be more excellent.
  • At least part of the above mono/diester may be contained in the form of a salt.
  • Salts include alkali metal salts, alkylamine salts, alkanolamine salts, quaternary ammonium salts and the like.
  • Alkali metals that make up alkali metal salts include sodium, potassium, lithium, rubidium, and cesium.
  • alkylamines constituting alkylamine salts include trimethylamine, triethylamine, dibutylamine, and butyldimethylamine.
  • alkanolamines constituting alkanolamine salts include dimethylmonoethanolamine, methyldiethanolamine, monoethanolamine, diethanolamine, triethanolamine, and isopropylethanolamine.
  • the ratio (mass ratio) of the phosphate monoester or its salt and the phosphate diester or its salt is not particularly limited.
  • the ratio of phosphoric acid monoester or its salt to phosphoric acid diester or its salt is 0:100 to 100:0, preferably 10:90 to 90:10, more preferably 20:80. ⁇ 80:20.
  • the content of the mono/diester or salt thereof may be appropriately adjusted according to the use of the composition.
  • the antibacterial/antiviral agent composition according to the present embodiment may contain at least one of the monoester or salt thereof and the diester or salt thereof, and may contain both. may The details of the component contents in the composition will be described later.
  • the antibacterial/antiviral agent composition according to the present embodiment may contain other ingredients in addition to the above mono/diester or salt thereof.
  • Other components include, for example, water and organic solvents.
  • various resins described later may be contained as other components.
  • various additives may be contained as other components.
  • the antibacterial/antiviral agent composition according to the present embodiment may contain other antiviral components in addition to the above mono/diester or salt thereof.
  • the antibacterial/antiviral agent composition according to this embodiment may contain only the above mono/diester or a salt thereof as an antiviral component.
  • the above mono/diester or a salt thereof and optionally a resin may be used and treated in an aqueous system.
  • it may be treated in a non-aqueous system (including the case where an organic solvent is used and the case where no solvent is used).
  • Resins used together with mono/diesters or salts thereof include, for example, compounds having a radically polymerizable carbon-carbon double bond, epoxy compounds, melamine compounds, phenol compounds, oxetane resins, urea resins, acrylic resins, urethane resins, Polyester resin, ethylene vinyl acetate resin, styrene-butadiene rubber, vinyl chloride resin, silicone resin, acrylic silicone copolymer resin, polyolefin resin, acrylonitrile butadiene rubber (NBR), chlorinated polyolefin resin and the like. These resins may be used alone or in combination of two or more. Preferred components contained in the antibacterial/antiviral agent composition according to the present embodiment are exemplified below for both cases of aqueous treatment and non-aqueous treatment.
  • Water-based polyurethane resin For various structures, water-based In the case of treating with, it is preferable to use a water-based polyurethane resin as the resin.
  • the antibacterial/antiviral agent composition according to this embodiment may contain the above mono/diester or a salt thereof, a water-based polyurethane resin, and water.
  • the aqueous polyurethane resin has, for example, a polyisocyanate compound, a polyol compound, an anionic group (at least one of a carboxyl group, a carboxylate group, a sulfo group, a sulfonate group, etc.) and two or more active hydrogens.
  • compound, the neutralized product of the isocyanate group-terminated prepolymer obtained by reacting with is emulsified and dispersed in water (hereinafter, dispersing or emulsifying is referred to as "emulsification dispersion"), and then an amine-based chain extender is added. obtained by a chain elongation reaction in water.
  • the water-based polyurethane resin referred to in the present application means a polyurethane resin having emulsifying dispersibility in water.
  • the water-based polyurethane resin referred to in the present application is obtained by preparing an emulsified dispersion (solvent: water) having a polyurethane resin concentration of 35% by mass, and then exposing the emulsified dispersion at atmospheric pressure to 20°C. Separation or sedimentation is not observed even after standing for 12 hours at room temperature.
  • the polyisocyanate compound that constitutes the aqueous polyurethane resin is not particularly limited, and examples thereof include aromatic polyisocyanate compounds, aliphatic polyisocyanate compounds, and alicyclic polyisocyanate compounds.
  • aromatic polyisocyanate compounds include toluene diisocyanate (TDI), xylylene diisocyanate (XDI), diphenylmethane diisocyanate (MDI), naphthalene diisocyanate (NDI), and tetramethylxylylene diisocyanate.
  • aliphatic polyisocyanate compounds include hexamethylene diisocyanate (HDI).
  • alicyclic polyisocyanate compounds examples include 1,3-bis(isocyanatomethyl)cyclohexane, isophorone diisocyanate (IPDI), dicyclohexylmethane diisocyanate (H12MDI) and norbornane diisocyanate. These polyisocyanate compounds can be used singly or in combination of two or more. Among such polyisocyanates, aliphatic polyisocyanates and alicyclic polyisocyanate compounds can impart non-yellowing properties to substrates.
  • At least one of hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, norbornane diisocyanate and 1,3-bis(isocyanatomethyl)cyclohexane is particularly preferred.
  • the polyol compound that constitutes the water-based polyurethane resin is not particularly limited, and examples include polyether polyol, polyester polyol, and polycarbonate polyol. These polyol compounds can be used singly or in combination of two or more. In particular, when polycarbonate polyol is used, abrasion resistance is improved.
  • the number average molecular weight of the polyol compound is not particularly limited, it may be, for example, 1,000 or more and 3,000 or less. When the number average molecular weight is within this range, the appearance quality and wear resistance are improved.
  • Polyether polyols include, for example, homo-addition polymers or co-addition polymers of alkylene oxides having 2 to 4 carbon atoms such as ethylene oxide, propylene oxide and tetramethylene oxide (block copolymerization or random copolymerization may be used). A polyol and the like can be mentioned.
  • polycarbonate polyols include those obtained by dealcoholization reaction and dephenolation reaction between polyols and carbonates.
  • Polyols are, for example, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol , 1,6-hexanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 1,8-octanediol, 1,9-nonanediol, diethylene glycol, dipropylene glycol, 1,4-cyclohexanedimethanol , or one or more selected from ethylene oxide or propylene oxide adducts of bisphenol A and the like.
  • the carbonates may be, for example, one or more selected from diethyl carbonate, dimethyl carbonate,
  • polyester polyols include those obtained by a polycondensation reaction between a dibasic acid and the above polyols.
  • Dibasic acid is selected from, for example, phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, succinic acid, malonic acid, adipic acid, sebacic acid, 1,4-cyclohexyldicarboxylic acid, maleic acid, fumaric acid, etc.
  • phthalic acid is selected from, for example, phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, succinic acid, malonic acid, adipic acid, sebacic acid, 1,4-cyclohexyldicarboxylic acid, maleic acid, fumaric acid, etc.
  • the above polyester polyols may be used singly or in combination of two or more.
  • compounds having at least one of a carboxyl group and a carboxylate group include, for example, 2,2-dimethylolpropionic acid , 2,2-dimethylolbutanoic acid, and salts thereof.
  • a polyester polyol having a pendant carboxyl group obtained by reacting a diol compound having a carboxyl group with an aromatic dicarboxylic acid, an aliphatic dicarboxylic acid, or the like can also be used.
  • the diol compound having a carboxyl group may be mixed with a diol compound having no carboxyl group as a diol component and reacted.
  • compounds having at least one of a sulfo group and a sulfonate group include, for example, 3,4-diaminobutanesulfonic acid, 3,6-diamino-2-toluenesulfonic acid, 2-(2-aminoethylamino)ethanesulfonic acid, ethylenediaminepropylsulfonic acid, ethylenediaminebutylsulfonic acid, 1,2- or 1,3-propylenediamine- ⁇ -ethyl sulfonic acids, diaminosulfonic acids such as 2-(3-aminopropylamino)-ethanesulfonic acid, 2,4-diaminobenzenesulfonic acid; and salts thereof.
  • These compounds can be used individually by 1 type or in combination of 2 or more types.
  • the content of anionic groups in the aqueous polyurethane resin is not particularly limited.
  • the aqueous polyurethane resin contains at least one anionic group of 0.5% by mass or more and 4.0% by mass. % or less.
  • the total content of the anionic groups may be 0.5% by mass or more and 4.0% by mass or less.
  • the contents of carboxyl groups and carboxylate groups can be obtained by calculating the amount of COO per 100 g of polyurethane resin from the amount of charged raw materials.
  • the content of sulfo groups and sulfonate groups can be obtained by calculating the amount of SO 3 per 100 g of polyurethane resin from the amount of raw materials charged.
  • the content of the anionic group is 4.0% by mass or less, the texture becomes softer and the problem of whitening during bending can be more easily suppressed.
  • the content of the anionic group is 0.5% by mass or more, the storage stability of the aqueous polyurethane resin is improved, and more stable processing becomes possible.
  • low-molecular-weight polyhydric alcohols such as ethylene glycol, 1,4-butanediol, and hexamethylene glycol may be used as polyol compounds.
  • chain extenders examples include ethylenediamine, propylenediamine, tetramethylenediamine, hexamethylenediamine, hydrazine, 4,4'-diaminodicyclohexylmethane, piperazine, 2-methylpiperazine, isophoronediamine, norboranediamine, diaminodiphenylmethane, tri Low molecular weight polyamines such as diamine, xylylenediamine, diethylenetriamine, triethylenetetramine, triethylenetetramine, tetraethylenepentamine, iminobispropylamine (at least one selected from the group consisting of primary amino groups and secondary amino groups) polyamine compounds containing two or more of the above amino groups in one molecule). These chain extenders can be used singly or in combination of two or more.
  • the water-based polyurethane resin may be, for example, a flame retardant-blended urethane resin containing a phosphorus compound as a flame retardant component disclosed in JP-A-2006-206839.
  • the specific method for producing the above-mentioned isocyanate group-terminated prepolymer is not particularly limited, and for example, it can be produced by a conventionally known one-stage so-called one-shot method, a multi-stage isocyanate polyaddition reaction method, or the like.
  • the reaction temperature at this time is preferably 40 to 150°C.
  • an organic solvent that does not react with isocyanate groups may be added during or after the reaction.
  • an organic solvent for example, acetone, methyl ethyl ketone, toluene, tetrahydrofuran, etc. can be used.
  • dibutyltin dilaurate stannous octoate, dibutyltin di-2-ethylhexoate, triethylamine, triethylenediamine, N-methylmorpholine, bismath tris (2-ethylhexanoate) or a reaction inhibitor such as phosphoric acid, sodium hydrogen phosphate, p-toluenesulfonic acid, adipic acid and benzoyl chloride.
  • the content of residual isocyanate groups in the isocyanate group-terminated prepolymer is preferably 0.2 to 4.5% by mass. Within this range, the film formability of the water-based polyurethane resin composition obtained by subsequent chain extension with polyamine is good, and the formed film is soft and exhibits appropriate flexibility. Incidentally, the residual isocyanate group content can be obtained by the following method.
  • 0.3 g of the resulting urethane prepolymer is placed in an Erlenmeyer flask, mixed with 10 ml of 0.1N dibutylamine toluene solution, and dissolved. Then, several drops of bromophenol blue solution are added, titration is performed with a 0.1N hydrochloric acid methanol solution, and the free isocyanate group content NCO% can be determined by the following formula.
  • NCO % (ab) x 0.42 x f/x a: Titration amount of 0.1N hydrochloric acid methanol solution when only 10 ml of 0.1N dibutylamine toluene solution was titrated b: Titration amount of 0.1N hydrochloric acid methanol solution when titrating the composition during reaction f: 0. Factor x of 1N hydrochloric acid methanol solution: Amount of sampling.
  • the isocyanate group-terminated prepolymer has an appropriate viscosity and is easily emulsified.
  • the texture of the structure treated with the antibacterial/antiviral agent composition can be made softer, and whitening during bending can be more easily prevented.
  • Neutralization of the anionic groups of the isocyanate group-terminated prepolymer can be carried out using a suitable known method before, during or after the preparation of the isocyanate group-terminated prepolymer.
  • the compound used for neutralizing the isocyanate group-terminated prepolymer having such an anionic group examples include trimethylamine, triethylamine, tri-n-propylamine, tributylamine, N-methyl-diethanolamine, Examples include amines such as N-dimethylmonoethanolamine, N,N-diethylmonoethanolamine and triethanolamine, potassium hydroxide, sodium hydroxide and ammonia.
  • tertiary amines such as trimethylamine, triethylamine, tri-n-propylamine and tributylamine are particularly preferred.
  • the emulsifying and dispersing equipment used when emulsifying and dispersing the neutralized isocyanate group-terminated prepolymer in water there are no particular restrictions on the emulsifying and dispersing equipment used when emulsifying and dispersing the neutralized isocyanate group-terminated prepolymer in water, and examples include homomixers, homogenizers, and dispersers. Further, when emulsifying and dispersing the neutralized isocyanate group-terminated prepolymer in water, the neutralized isocyanate group-terminated prepolymer is emulsified and dispersed in water in a temperature range of 0 to 40 ° C., and the isocyanate group and It is preferable to suppress the reaction with water as much as possible.
  • reaction inhibitors such as phosphoric acid, sodium dihydrogen phosphate, disodium hydrogen phosphate, paratoluenesulfonic acid, adipic acid, and benzoyl chloride can be added as necessary. .
  • the isocyanate group-terminated prepolymer emulsified and dispersed in water uses a polyamine compound containing two or more amino groups per molecule of at least one selected from the group consisting of primary amino groups and secondary amino groups. May be chain extended.
  • the reaction between the isocyanate group-terminated prepolymer and the polyamine compound is completed at a reaction temperature of 20 to 50° C. usually in 30 to 120 minutes.
  • the above-mentioned organic solvent when producing the isocyanate group-terminated prepolymer, it is desirable to distill off the organic solvent at 30 to 80°C under reduced pressure, for example, after the chain extension reaction or emulsification and dispersion.
  • An emulsified dispersion of a water-based polyurethane resin can be obtained by such a preparation method.
  • the resin solid content (non-volatile content) concentration in the emulsified dispersion of the water-based polyurethane resin may be, for example, 20% or more and 60% or less.
  • the resin solid content concentration can also be adjusted by adding or distilling off water.
  • the antibacterial/antiviral agent composition according to the present embodiment may contain the above mono/diester or a salt thereof, a water-based acrylic resin, and water. You may use together with resin.
  • a water-based polyurethane resin and a water-based acrylic resin are used together, the mass ratio is not particularly limited. may be:
  • Examples of the monomer constituting the water-based acrylic resin include (meth)acrylates having a hydroxyl group, and (meth)acrylates having a carboxyl group which are reaction products of a (meth)acrylate having a hydroxyl group and a dicarboxylic acid or a derivative thereof. .
  • Examples of (meth)acrylates having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3 - hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, glycerin mono(meth)acrylate, glycerin di(meth)acrylate, trimethylolpropane mono(meth)acrylate, trimethylolpropane di(meth)acrylate, penta Erythritol mono (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, neopentyl glycol mono (meth) acrylate, and the like.
  • dicarboxylic acid examples include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid and the like.
  • hydroxyl-containing (meth)acrylates and dicarboxylic acids may be used singly or in combination of two or more.
  • (meth)acrylate is a generic term for acrylate and methacrylate, and means one or both of acrylate and methacrylate.
  • the content of the water-based resin (water-based polyurethane resin or water-based acrylic resin) is not particularly limited.
  • the water-based antibacterial/antiviral agent composition may contain the water-based resin in an amount of 0.01% by mass or more or 0.02% by mass or more, and may contain 50% by mass or less or 20% by mass or less. .
  • the composition after dilution contains the water-based resin in an amount of 0.001% by mass or more, 0.005% by mass or more, or It may be contained in an amount of 0.1% by mass or more, and may be contained in an amount of 20% by mass or less or 10% by mass or less.
  • additives may be contained in the water-based antibacterial/antiviral agent composition.
  • it may contain emulsifiers, thickeners, preservatives, buffers, pH adjusters, leveling agents, fillers, antifoaming agents and the like.
  • thickeners include alkali-thickened acrylic resins, associative thickeners, and water-soluble organic polymers. These thickeners may be used alone or in combination of two or more. A commercially available one can be used as the alkali-thickening acrylic resin.
  • alkali-thickening acrylic resins examples include Nikasol VT-253A (manufactured by Nippon Carbide Industry Co., Ltd.), Aron A-20P, Aron A-7150, Aron A-7070, Aron B-300, and Aron B.
  • the content of the above mono/diester or salt thereof in the water-based antibacterial/antiviral agent composition is not particularly limited.
  • the water-based antibacterial/antiviral composition may contain 0.01% by mass or more or 0.02% by mass or more of the above mono/diester or a salt thereof, and 50% by mass or less or 20% by mass or less. may contain.
  • the antibacterial/antiviral agent composition is used after being diluted with a solvent such as water, the diluted composition contains 0.001% by mass or more and 0.002% by mass of the above mono/diester or salt thereof. % or more, 0.01 mass % or more, or 0.02 mass % or more, and may contain 5 mass % or less, or 4 mass % or less.
  • Non-Aqueous Antibacterial/Antiviral Agent Compositions (1) Curing Components Various structures are treated with the above mono/diesters or salts thereof in a non-aqueous system.
  • the curing component may be used with the above mono/diesters or salts thereof.
  • the antibacterial/antiviral agent composition according to this embodiment contains the above mono/diester or salt thereof, a curing component, and optionally a solvent (organic solvent).
  • the curing component include a thermosetting component, an active energy ray curing component, and the like, which will be described later.
  • thermosetting component is at least one selected from the group consisting of thermosetting compounds and thermosetting resins.
  • a thermosetting compound means a compound having a characteristic of reacting and curing by heating, for example, a prepolymer having a polymerizable functional group that polymerizes by heating in the presence of a polymerization initiator, a curing agent, or the like. Examples include thermosetting monomers and oligomers that are cured (cross-linked) by heating in the presence of a cross-linking agent.
  • thermosetting resin means that the thermosetting compound is polymerized (cured) by heating, for example, a polymer obtained by polymerizing the prepolymer having the polymerizable functional group, the thermosetting monomer or A cured product or a semi-cured product of an oligomer may be mentioned.
  • a prepolymer obtained by thermally polymerizing a monomer having a polymerizable functional group can be used as a thermosetting resin as it is without using a polymerization initiator.
  • thermosetting component is a concept that includes both the thermosetting compound and the thermosetting resin.
  • thermosetting resin is not particularly limited, but for example, (I) Copolymerizing a monomer having a polymerizable functional group with another monomer, or introducing a polymerizable functional group into a polymer chain constituting the prepolymer to prepare a prepolymer having the polymerizable functional group.
  • thermosetting monomer or oligomer by heating in the presence of a curing agent or crosslinking agent to obtain a cured or semi-cured product of the thermosetting monomer or oligomer.
  • thermosetting compound examples include compounds having radically polymerizable carbon-carbon double bonds, epoxy compounds, melamine compounds, phenol compounds, oxetane resins, urea resins, acrylic resins, urethane resins, polyester resins, and ethylene acetic acid. vinyl resin, styrene-butadiene rubber, and the like. These thermosetting compounds may be used alone or in combination of two or more. Among these thermosetting compounds, acrylic resins, urethane resins, polyester resins, ethylene vinyl acetate resins, and styrene-butadiene rubbers can also be used as thermosetting resins. Acrylic resins, urethane resins, polyester resins, ethylene vinyl acetate resins, and styrene-butadiene rubbers (that is, thermosets thereof) after curing can also be used as thermosetting resins.
  • thermosetting component is preferably liquid at room temperature (25°C).
  • a compound having a radically polymerizable carbon-carbon double bond is a compound having a carbon-carbon double bond in the molecule. , is a compound that hardens when carbon-carbon double bonds react. In compounds having such a radically polymerizable carbon-carbon double bond, from the viewpoint of improving hardness, wear resistance, heat resistance, etc., a radically polymerizable carbon-carbon double bond is included in one molecule. Compounds with two or more are preferred.
  • Compounds having radically polymerizable carbon-carbon double bonds include, for example, polyethers, polyesters, polycarbonates, poly(meth)acrylates, polybutadiene or butadiene acrylonitrile copolymers having acrylic groups; polyethers, Polyester, polycarbonate, poly(meth)acrylate, polybutadiene or butadiene-acrylonitrile copolymer having an allyl group; a compound having a maleimide group; a thermally reactive monomer;
  • Preferred radically polymerizable carbon-carbon double bond compounds are exemplified below, but the radically polymerizable carbon-carbon double bond compound used in the antibacterial/antiviral agent composition is limited to these. not something.
  • polyether polyester, polycarbonate, poly(meth)acrylate, polybutadiene or butadiene-acrylonitrile copolymer compound having an acrylic group
  • a polyether in which organic groups having 3 to 6 carbon atoms are repeated through ether bonds is preferable.
  • a polyether having such an acrylic group can be obtained by reacting a polyether polyol with (meth)acrylic acid or a derivative thereof.
  • polyester constituting the acrylic group-containing polyester those in which organic groups having 3 to 6 carbon atoms are repeated via ester bonds are preferable.
  • a polyester having such an acrylic group can be obtained by reacting a polyester polyol with (meth)acrylic acid or a derivative thereof.
  • polycarbonate constituting a polycarbonate having an acrylic group one in which organic groups having 3 to 6 carbon atoms are repeated via carbonate bonds is preferable.
  • a polycarbonate having acrylic groups can be obtained by reacting a polycarbonate polyol with (meth)acrylic acid or a derivative thereof.
  • Poly(meth)acrylates constituting poly(meth)acrylates having acrylic groups include copolymers of (meth)acrylic acid and (meth)acrylates, and (meth)acrylates having hydroxyl groups and having no polar groups.
  • a copolymer with (meth)acrylate, a copolymer of (meth)acrylate having a glycidyl group and (meth)acrylate having no polar group, and the like are preferable.
  • Poly (meth) acrylate having such an acrylic group is a copolymer having a carboxy group (for example, a copolymer of (meth) acrylic acid and (meth) acrylate) and a (meth) acrylate having a hydroxyl group or glycidyl Reaction with (meth)acrylate having a group, a copolymer having a hydroxyl group (e.g., a copolymer of a (meth)acrylate having a hydroxyl group and a (meth)acrylate having no polar group) and (meth)acrylic acid or a reaction with a derivative thereof, or a copolymer having a glycidyl group (for example, a copolymer of a (meth)acrylate having a glycidyl group and a (meth)acrylate having no polar group) and (meth)acrylic acid or by reaction with a derivative thereof.
  • Polybutadiene having an acrylic group is a reaction of a polybutadiene having a carboxyl group with a (meth)acrylate having a hydroxyl group or a (meth)acrylate having a glycidyl group, a reaction of a polybutadiene having a hydroxyl group with (meth)acrylic acid or a derivative thereof, Alternatively, it can be obtained by reacting polybutadiene to which maleic anhydride is added and a (meth)acrylate having a hydroxyl group.
  • a butadiene-acrylonitrile copolymer having an acrylic group can be obtained by reacting a butadiene-acrylonitrile copolymer having a carboxy group with a (meth)acrylate having a hydroxyl group or a (meth)acrylate having a glycidyl group.
  • Polyether polyester, polycarbonate, poly(meth)acrylate, polybutadiene or butadiene-acrylonitrile copolymer compound having an allyl group
  • compounds having an allyl group include reaction products of diallyl esters and diols.
  • diallyl esters include reaction products of dicarboxylic acids or derivatives thereof with allyl alcohol.
  • dicarboxylic acids examples include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, Azelaic acid, sebacic acid, maleic acid, fumaric acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid and the like.
  • diol examples include ethylene glycol, propylene glycol, tetramethylene glycol and the like.
  • Compounds having a maleimide group include, for example, N,N'-(4,4'-diphenylmethane)bismaleimide, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, 2,2-bis[4 -bismaleimide compounds such as (4-maleimidophenoxy)phenyl]propane; reaction products of dimer acid diamine and maleic anhydride; reaction products of maleimidated amino acids such as maleimidoacetic acid and maleimidocaproic acid with polyols; Among them, a reaction product of diamine dimer acid and maleic anhydride; a reaction product of maleimidated amino acid such as maleimidoacetic acid and maleimidocaproic acid and a polyol are preferable.
  • the maleimidated amino acid is obtained by reacting maleic anhydride with aminoacetic acid or aminocaproic acid.
  • Polyether polyols, polyester polyols, polycarbonate polyols, polyacrylate polyols, and polymethacrylate polyols are preferred as polyols.
  • thermally reactive monomers examples include hydroxyl group-containing (meth)acrylates and carboxyl group-containing (meth)acrylates that are reaction products of hydroxyl group-containing (meth)acrylates and dicarboxylic acids or derivatives thereof.
  • Examples of (meth)acrylates having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3 - hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, glycerin mono(meth)acrylate, glycerin di(meth)acrylate, trimethylolpropane mono(meth)acrylate, trimethylolpropane di(meth)acrylate, penta Erythritol mono (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, neopentyl glycol mono (meth) acrylate, and the like.
  • dicarboxylic acid examples include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid and the like.
  • hydroxyl-containing (meth)acrylates and dicarboxylic acids may be used singly or in combination of two or more.
  • the thermal radical polymerization initiator for the compound having a radically polymerizable carbon-carbon double bond is not particularly limited, but a rapid heating test (1 g of the sample was placed on an electric heating plate, and the temperature was raised at 4 ° C./min. It is preferable that the decomposition temperature is 40° C. or more and 140° C. or less in the decomposition start temperature when the decomposition is performed. When the decomposition temperature is less than the lower limit, the composition containing the radically polymerizable compound having a carbon-carbon double bond and the thermal radical polymerization initiator tends to have poor storage stability at room temperature. exceeds, the curing time tends to be extremely long.
  • thermal radical polymerization initiators include methyl ethyl ketone peroxide, methylcyclohexanone peroxide, methyl acetoacetate peroxide, acetylacetone peroxide, 1,1-bis(t-butylperoxy)3,3,5 -trimethylcyclohexane, 1,1-bis(t-hexylperoxy)cyclohexane, 1,1-bis(t-hexylperoxy)3,3,5-trimethylcyclohexane, 1,1-bis(t-butylperoxy) ) cyclohexane, 2,2-bis(4,4-di-t-butylperoxycyclohexyl)propane, 1,1-bis(t-butylperoxy)cyclododecane, n-butyl 4,4-bis(t- butylperoxy)valerate, 2,2-bis(t-butylperoxy)butane, 1,1-bis(t-butyl
  • Epoxy compounds are compounds having one or more glycidyl groups in the molecule, and are compounds that form a three-dimensional network structure and cure when the glycidyl groups react with heating. .
  • compounds containing two or more glycidyl groups in one molecule are preferable from the viewpoint of exhibiting sufficient cured product properties.
  • the epoxy compound is not particularly limited, but examples include bisphenol compounds such as bisphenol A, bisphenol F and biphenol, or derivatives thereof, hydrogenated bisphenol A, hydrogenated bisphenol F, hydrogenated biphenol, cyclohexanediol, cyclohexanedimethanol, Bifunctional compounds obtained by epoxidizing diols having an alicyclic structure such as cyclohexanediethanol or derivatives thereof, aliphatic diols such as butanediol, hexanediol, octanediol, nonanediol, decanediol, or derivatives thereof, trihydroxy Polyfunctional epoxy resins obtained by epoxidizing trifunctional compounds having a phenylmethane skeleton or aminophenol skeleton, phenol novolac resin, cresol novolak resin, phenol aralkyl resin, biphenyl aralkyl resin, naphthol aralkyl resin, and the
  • such epoxy compounds are preferably liquid at room temperature either singly or as a mixture.
  • an antibacterial/antiviral agent composition that is liquid at room temperature is obtained.
  • a method for epoxidizing a diol or a derivative thereof a method of epoxidizing by reacting two hydroxyl groups of the diol or a derivative thereof with epichlorohydrin to convert them into glycidyl ether, and the like can be mentioned.
  • an epoxy compound can be diluted with a reactive diluent before use.
  • reactive diluents include monofunctional aromatic glycidyl ethers such as phenyl glycidyl ether, tert-butyl phenyl glycidyl ether and cresyl glycidyl ether, and aliphatic glycidyl ethers.
  • curing agent for epoxy compound examples include aliphatic amines, aromatic amines, dicyandiamides, dihydrazide compounds, acid anhydrides, and phenol compounds.
  • dihydrazide compound examples include carboxylic acid dihydrazide such as adipic acid dihydrazide, dodecanoic acid dihydrazide, isophthalic acid dihydrazide, and p-oxybenzoic acid dihydrazide.
  • Examples of the acid anhydride include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, dodecenylsuccinic anhydride, and maleic anhydride. be done.
  • the phenol compound used as the curing agent for the epoxy compound is a compound having two or more phenolic hydroxyl groups in one molecule.
  • a compound having only one phenolic hydroxyl group in one molecule cannot form a crosslinked structure, resulting in deterioration of cured product properties.
  • the phenol compound may have two or more phenolic hydroxyl groups in one molecule, but preferably has two to five phenolic hydroxyl groups in one molecule. Those having two or three phenolic hydroxyl groups in the molecule are more preferable.
  • phenol compounds include bisphenol F, bisphenol A, bisphenol S, tetramethylbisphenol A, tetramethylbisphenol F, tetramethylbisphenol S, dihydroxydiphenyl ether, dihydroxybenzophenone, tetramethylbisphenol, ethylidenebisphenol, methylethylidenebis(methyl phenol), cyclohexylidenebisphenol, biphenol and other bisphenols and their derivatives, trifunctional phenols and their derivatives such as tri(hydroxyphenyl)methane and tri(hydroxyphenyl)ethane, reacting phenols with formaldehyde Phenol resins such as phenol novolak and cresol novolac obtained by the above and derivatives thereof.
  • formaldehyde Phenol resins such as phenol novolak and cresol novolac obtained by the above and derivatives thereof.
  • curing accelerators for the epoxy compounds include imidazoles, salts of triphenylphosphine or tetraphenylphosphonium, amine compounds such as diazabicycloundecene, and salts thereof.
  • these curing accelerators 2-methylimidazole, 2-ethylimidazole-2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenyl- Imidazole compounds such as 4,5-dihydroxymethylimidazole, 2-C 11 H 23 -imidazole, adducts of 2-methylimidazole and 2,4-diamino-6-vinyltriazine are preferred, and imidazoles having a melting point of 180° C. or higher Compounds are particularly preferred.
  • the melamine compound is melamine or a derivative thereof.
  • Derivatives of melamine include, for example, derivatives having functional groups such as imino groups, methylol groups, methoxymethyl groups, and alkoxymethyl groups such as butoxymethyl groups.
  • Specific examples of such melamine compounds include derivatives having a methylol group such as monomethylolmelamine, dimethylolmelamine, trimethylolmelamine, tetramethylolmelamine, pentamethylolmelamine, and hexamethylolmelamine.
  • Phenol compound A phenol compound is a compound having two or more phenolic hydroxyl groups in one molecule.
  • examples of the phenolic compound used in the present invention include the phenolic compounds exemplified as the curing agent for the epoxy compound.
  • Urethane resin is a reaction product of raw materials including polyol and polyisocyanate, and may be chain-extended if necessary.
  • a urethane resin is preferably a urethane resin having at least one functional group selected from a hydroxyl group, an amino group and an imino group.
  • a urethane resin having such a functional group can be obtained by using a polyol and a chain extender in an amount in which the total amount thereof exceeds the equivalent amount with respect to the polyisocyanate.
  • Each component of the raw material of the urethane resin will be described below.
  • a polyol is a compound having two or more hydroxyl groups in one molecule.
  • the polyol is not particularly limited, and examples thereof include polyether polyols, polycarbonate polyols, polyester polyols, polyether ester polyols, polyolefin polyols, silicon polyols, aliphatic polyols, alicyclic polyols, aromatic polyols, and the like. . These polyols may be used alone or in combination of two or more.
  • polycarbonate polyols are preferable from the viewpoint of improving the weather resistance, mechanical strength and wear resistance of the cured film.
  • the amount of polycarbonate polyol used relative to the total amount of polyol used is preferably 25 mol% or more, more preferably 50 mol% or more, and further preferably 70 mol% or more, from the viewpoint of improving the hardness and weather resistance of the cured film. preferable.
  • Polyether polyols include, for example, homo-addition polymers or co-addition polymers of alkylene oxides having 2 to 4 carbon atoms such as ethylene oxide, propylene oxide and tetramethylene oxide (block copolymerization or random copolymerization may be used).
  • a polyol and the like are exemplified.
  • polycarbonate polyols include those obtained by dealcoholization reaction and dephenolation reaction between polyols and carbonates.
  • Polyols include, for example, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentane Diol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, diethylene glycol, dipropylene glycol , 1,4-cyclohexanedimethanol, ethylene oxide or propylene oxide adducts of bisphenol A, and the like.
  • polyols may be used alone or in combination of two or more.
  • carbonates include diethyl carbonate, dimethyl carbonate, diphenyl carbonate and the like. These carbonates may be used individually by 1 type, or may use 2 or more types together. Polycarbonate polyols composed of combinations of such polyols and carbonates may be used singly or in combination of two or more.
  • polyester polyols include those obtained by a polycondensation reaction between a dibasic acid and the above-mentioned polyols.
  • dibasic acids include phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, succinic acid, malonic acid, adipic acid, sebacic acid, 1,4-cyclohexyldicarboxylic acid, maleic acid, fumaric acid, and the like. .
  • These dibasic acids may be used individually by 1 type, or may use 2 or more types together.
  • polyester polyols comprising a combination of dibasic acid and polyols may be used singly or in combination of two or more.
  • polyether ester polyols examples include compounds obtained by ring-opening polymerization of cyclic ethers in the above polyester polyols, and compounds obtained by polycondensing the above polyether polyols and the above dicarboxylic acids. Among them, poly(polytetramethylene ether) adipate. preferable.
  • a polyolefin polyol is a polyolefin having two or more hydroxyl groups.
  • the said polyolefin polyol may be used individually by 1 type, or may use 2 or more types together.
  • Examples of the polyolefin polyol include polybutadiene polyol, hydrogenated polybutadiene polyol, and polyisoprene polyol.
  • a silicone polyol is a silicone having two or more hydroxyl groups.
  • the silicone polyols may be used singly or in combination of two or more.
  • Examples of the silicone polyol include polydimethylsiloxane polyol.
  • aliphatic polyols examples include ethylene glycol, propylene glycol, 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, neopentyl glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 2-methyl-1,5-pentanediol, 3-methyl-1,5-pentanediol, 2,2,4-trimethyl -1,5-pentanediol, 2,3,5-trimethyl-1,5-pentanediol, 1,6-hexanediol, 2-ethyl-1,6-hexanediol, 2,2,4-trimethyl-1 ,6-hexanediol, 3,3-dimethylolheptane, 1,8-octanediol,
  • Alicyclic polyols include cyclopropanediol, cyclopropanedimethanol, cyclopropanediethanol, cyclopropanedipropanol, cyclopropanedibutanol, cyclopentanediol, cyclopentanedimethanol, cyclopentanediethanol, cyclopentanedipropanol, cyclopentane Dibutanol, cyclohexanediol, cyclohexanedimethanol, cyclohexanediethanol, cyclohexanedipropanol, cyclohexanedibutanol, cyclohexenediol, cyclohexenedimethanol, cyclohexenediethanol, cyclohexenedipropanol, cyclohexenedibutanol, cyclohexadienediol, cyclohexa
  • ethylene glycol, propylene glycol, 1,2-propanediol, and 1,3-propanediol are used from the viewpoint of improving the weather resistance and mechanical strength of the resulting cured film.
  • aromatic polyols examples include bishydroxyethoxybenzene, bishydroxyethyl terephthalate, and bisphenol-A.
  • dialkanolamines such as N-methyldiethanolamine; pentaerythritol; sorbitol; mannitol; glycerin; trimethylolpropane, etc. can also be used as other polyol components.
  • polyisocyanate A polyisocyanate is a compound having one or both of two or more isocyanate groups and substituents containing isocyanate groups (also referred to as "isocyanate groups") in one molecule. Polyisocyanate may be used individually by 1 type, or may use 2 or more types together. It may also be a polymer of polyisocyanate (a modified product obtained by reacting polyisocyanate monomers with each other). Furthermore, in one polyisocyanate, the isocyanate groups may be the same or different.
  • polyisocyanate may be modified with urethane, urea, buret, allophanate, carbodiimide, oxazoline, amide, imide, polyol and the like.
  • polynuclear isomers may contain isomers other than these.
  • substituents containing an isocyanate group include alkyl groups, alkenyl groups, or alkoxyl groups containing one or more isocyanate groups and having 1 to 5 carbon atoms.
  • the number of carbon atoms in the alkyl group or the like as a substituent containing an isocyanate group is preferably 1 to 3.
  • polyisocyanate examples include aliphatic polyisocyanate, polyisocyanate having an alicyclic structure, and aromatic polyisocyanate.
  • An aliphatic polyisocyanate is a compound having an aliphatic structure and two or more isocyanate groups bonded thereto. Aliphatic polyisocyanates are preferable from the viewpoint of enhancing the weather resistance of the cured film and imparting flexibility.
  • the aliphatic structure in the aliphatic polyisocyanate is not particularly limited, but a linear or branched alkylene group having 1 to 6 carbon atoms is preferred.
  • aliphatic polyisocyanates examples include methylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, propylene diisocyanate, and lysine diisocyanate.
  • aliphatic diisocyanates such as dimer diisocyanate obtained by converting the carboxyl group of dimer acid to an isocyanate group
  • aliphatic triisocyanates such as tris(isocyanatohexyl)isocyanurate.
  • hexamethylene diisocyanate is preferred.
  • the polyisocyanate preferably has an alicyclic structure in terms of the mechanical strength and stain resistance of the cured film.
  • a polyisocyanate having an alicyclic structure is a compound having an alicyclic structure and two or more isocyanate groups bonded thereto.
  • the alicyclic structure in the polyisocyanate having an alicyclic structure is not particularly limited, a cycloalkylene group having 3 to 6 carbon atoms is preferred.
  • polyisocyanates having an alicyclic structure examples include bis(isocyanatomethyl)cyclohexane, cyclohexanediisocyanate, bis(isocyanatocyclohexyl)methane, bis(isocyanatocyclohexyl)propane, isophorone diisocyanate, methylcyclohexane diisocyanate (hydrogenated TDI:), and the like. and triisocyanates having an alicyclic structure such as tris(isocyanatoisophorone)isocyanurate.
  • polyisocyanates having an alicyclic structure from the viewpoint of increasing the strength and adhesiveness of the cured film, from the viewpoint of less coloring over time, and from the viewpoint of being suitable for materials that require transparency, Bis(isocyanatomethyl)cyclohexane, cyclohexane diisocyanate, bis(isocyanatocyclohexyl)methane, and isophorone diisocyanate are preferred.
  • Aromatic polyisocyanates are compounds having an aromatic structure and two or more isocyanate groups bonded thereto. Although the aromatic structure in the aromatic polyisocyanate is not particularly limited, a divalent aromatic group having 6 to 13 carbon atoms is preferred. Examples of such aromatic polyisocyanates include xylylene diisocyanate, 4,4′-diphenyl diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4'-diphenylmethane diisocyanate (4,4'-MDI), 2,4'-diphenylmethane diisocyanate (2,4'-MDI), 4,4'-diphenyldimethylmethane diisocyanate, 4,4'-dibenzyl diisocyanate , dialkyldiphenylmethane diisocyanate, tetraalkyldipheny
  • Chain extenders are mainly classified into compounds having two or more hydroxyl groups (short-chain polyols), compounds having two or more amino groups (polyamine compounds), and water. Among these, water is preferably reduced as much as possible in order to stably carry out the reaction.
  • Compounds having two or more hydroxyl groups include, for example, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,3-propanediol, 1,2-butanediol, 1, 3-butanediol, 1,4-butanediol, 2,3-butanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 2-methyl-1,3-propanediol, 2-methyl-2 -propyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,5-pentanediol, 1,6-hexanediol, 2-methyl-2,4-pentanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-1,3-hexan
  • Examples of compounds having two or more amino groups include aromatic diamines such as 2,4- or 2,6-tolylenediamine, xylylenediamine, 4,4'-diphenylmethanediamine, ethylenediamine, 1,2- propylenediamine, 1,6-hexanediamine, 2,2-dimethyl-1,3-propanediamine, 2-methyl-1,5-pentanediamine, 1,3-diaminopentane, 2,2,4- or 2, Aliphatic diamines such as 4,4-trimethylhexanediamine, 2-butyl-2-ethyl-1,5-pentanediamine, 1,8-octanediamine, 1,9-nonanediamine, 1,10-decanediamine, 1- Amino-3-aminomethyl-3,5,5-trimethylcyclohexane (IPDA), 4,4'-dicyclohexylmethanediamine (hydrogenated MDA), isopropylidenecyclohexyl-4,4'-d
  • Chain terminating agent for the purpose of controlling the molecular weight of the urethane resin, a chain terminating agent having one active hydrogen group can be used, if necessary.
  • chain terminators aliphatic monools such as ethanol, propanol, butanol, hexanol, and the like, and one hydroxyl group as an active hydrogen group, and one amino group are included as chain terminators.
  • Chain terminators include aliphatic monoamines such as diethylamine, dibutylamine, monoethanolamine, and diethanolamine. These chain terminators may be used alone or in combination of two or more.
  • the method for producing the urethane resin is not particularly limited, and known methods generally used experimentally/industrially can be adopted. Specifically, (1) a method of reacting a polyol, a polyisocyanate and a chain extender together (one-step method), and (2) first, a polyol and a polyisocyanate are reacted to obtain a prepolymer having isocyanate groups at both ends. and then reacting this prepolymer with a chain extender (two-step method).
  • This two-step method includes a step of reacting a polyol with one or more equivalents of polyisocyanate in advance to prepare an intermediate (prepolymer) in which both ends corresponding to the soft segments of the urethane resin are blocked with isocyanate groups. It is a way to go through. By preparing a prepolymer in advance and then reacting it with a chain extender, it is easy to adjust the molecular weight of the soft segment part, and the phase separation between the soft segment and the hard segment is easily achieved, and it is easy to demonstrate the performance as a urethane resin. Characteristic.
  • the chain extender is a diamine
  • the reaction rate with the isocyanate group is significantly different from that with the hydroxyl group of the polyol, so it is more preferable to carry out polyurethane urea formation by a two-step method (prepolymer method).
  • the one-step method which is also called a one-shot method, is a method in which a polyol, a polyisocyanate and a chain extender are charged together to carry out the reaction.
  • the reaction temperature in the one-step process is usually 0 to 250° C., but can be appropriately set depending on the amount of solvent, reactivity of raw materials used, reaction equipment and the like. If the reaction temperature is too low, the reaction progresses too slowly and the solubility of the raw materials and polymer tends to decrease, resulting in a decrease in productivity. It may happen. Also, the reaction may be carried out while defoaming under reduced pressure. Furthermore, catalysts, stabilizers and the like may be added as necessary.
  • catalysts include triethylamine, tributylamine, dibutyltin dilaurate, stannous octoate, acetic acid, phosphoric acid, sulfuric acid, hydrochloric acid, sulfonic acid, etc.
  • Stabilizers include, for example, 2,6-dibutyl -4-methylphenol, distearylthiodipropionate, di ⁇ -naphthylphenylenediamine, tri(dinonylphenyl)phosphite and the like.
  • the two-stage method is also called a prepolymer method, in which a prepolymer is produced by reacting a polyisocyanate and a polyol in advance, usually at a reaction equivalent ratio of 1.0 to 10.00, and then polyisocyanate or polyol is added thereto. It is a method of reacting in two stages by adding a compound having active hydrogen such as a hydric alcohol or an amine.
  • a method of preparing a prepolymer containing isocyanate groups at both ends by reacting a polyisocyanate in an equivalent amount or more with a polyol, and then reacting the prepolymer with a chain extender such as a short-chain diol or diamine to obtain a urethane resin. is useful.
  • a prepolymer may be synthesized by directly reacting a polyisocyanate and a polyol without using a solvent, and a chain extender may act as it is, or (2) the above ( A prepolymer may be synthesized by the method of 1), then the prepolymer may be dissolved in a solvent and then treated with a chain extender, or (3) a polyisocyanate and a polyol may be reacted in a solvent to produce a prepolymer. may be synthesized and directly reacted with a chain extender in a solvent. In the method (2), the chain extender may be dissolved in the solvent and then acted on the prepolymer, or the chain extender may be dissolved at the same time as the prepolymer is dissolved in the solvent. .
  • the reaction temperature in the two-step method is usually 0 to 250°C, but can be appropriately set depending on the amount of solvent, the reactivity of the raw materials used, the reaction equipment, and the like. If the reaction temperature is too low, the reaction progresses too slowly and the solubility of the raw materials and polymer tends to decrease, resulting in a decrease in productivity. It may happen. Also, the reaction may be carried out while defoaming under reduced pressure. Furthermore, catalysts, stabilizers and the like may be added as necessary.
  • catalysts include triethylamine, tributylamine, dibutyltin dilaurate, stannous octoate, acetic acid, phosphoric acid, sulfuric acid, hydrochloric acid, sulfonic acid, etc.
  • Stabilizers include, for example, 2,6-dibutyl -4-methylphenol, distearylthiodipropionate, di ⁇ -naphthylphenylenediamine, tri(dinonylphenyl)phosphite and the like.
  • the chain extender is highly reactive such as a short-chain aliphatic amine, it is preferable to carry out the reaction without adding a catalyst.
  • a solvent can be used for the purpose of adjusting the viscosity.
  • Solvents may be used alone or in combination of two or more, and any known solvent can be used. Examples of such solvents include aliphatic hydrocarbon solvents such as hexane, cyclohexane, methylcyclohexane, ethylcyclohexane, heptane, nonane, octane, isooctane, and decane; aromatic hydrocarbon solvents such as benzene, toluene, xylene, cumene, and ethylbenzene; hydrogen; ester solvents such as ethyl acetate and butyl acetate; ether solvents such as diethyl ether, diisopropyl ether and methyl-tert-butyl ether; ketone solvents such as cyclohexanone, methyl
  • toluene, xylene, ethyl acetate, butyl acetate, cyclohexanone, methyl ethyl ketone, and methyl isobutyl ketone are preferred.
  • thermosetting compound contained in the antibacterial/antiviral agent composition is at least one of a hydroxyl group, an amino group, and an imino group.
  • a thermosetting compound having a functional group is preferable, and the urethane resin having the functional group, the acrylic resin having the functional group, the polyester resin having the functional group, the ethylene vinyl acetate resin having the functional group, the functional group styrene-butadiene rubber having a functional group, epoxy resin having the above functional group is more preferable, urethane resin having a hydroxyl group, acrylic resin having a hydroxyl group, polyester resin having a hydroxyl group, ethylene vinyl acetate resin having a hydroxyl group, styrene-butadiene rubber having a hydroxyl group , hydroxyl group-containing epoxy resins are more preferred, and hydroxyl group-containing urethane resins, hydroxyl group-containing acrylic resins, hydroxyl group-containing polyester
  • thermosetting compounds having a hydroxyl group include, for example, acrylic resins manufactured by Toray Fine Chemicals Co., Ltd. (trade names “Kotax LH-601” and “Kotax LH-591”), acrylic resins manufactured by Mitsui Chemicals, Inc. (trade names “Almatex 646”, “Almatex 646SB”, “Orester Q810”, “Orester Q519”), acrylic resin manufactured by DIC Corporation (trade name “Acrydic A-811”), manufactured by DIC Corporation Examples include polyester resin (trade name “Barnock D-161”), urethane resin (trade name “Polyurex Eco V-HK500 Clear P liquid (main agent)”) manufactured by Wasin Chemical Industry Co., Ltd., and the like.
  • thermosetting compound having a functional group examples include isocyanate curing agents, epoxy curing agents, melamine curing agents, and oxazoline curing agents. be done.
  • the isocyanate-based curing agent is a polyisocyanate having two or more isocyanate groups in one molecule.
  • isocyanate-based curing agents include monomers and modified polyisocyanates exemplified as raw materials for the urethane resin, and among them, aliphatic polyisocyanates and polymers thereof are preferred. These polyisocyanates may be used alone or in combination of two or more.
  • the epoxy-based curing agent is a crosslinkable epoxy compound having two or more glycidyl groups in one molecule.
  • examples of such an epoxy-based curing agent include those exemplified as the epoxy compounds. Among them, bisphenol A type liquid epoxy resin, alicyclic epoxy compound, and trimethylolpropane polyglycidyl ether are preferable.
  • the bisphenol A liquid epoxy resin is not particularly limited as long as it is liquid at room temperature, and commercially available products may be used.
  • commercial products include EPICLON840, 840-S, 850, 850-S, EXA-850CRP, 850-LC (trade name, manufactured by DIC Corporation), jER828EL, 827 (trade name, Mitsubishi Chemical Corporation (manufactured by Mitsui Chemicals, Inc.) and Epomic R-140P (trade name, manufactured by Mitsui Chemicals, Inc.).
  • the alicyclic epoxy compound is a compound having two or more epoxycycloalkyl groups or epoxycycloalkenyl groups in the molecule, or two groups in which at least one epoxy group is bonded to an alicyclic ring by a single bond. It is a compound having one or more.
  • alicyclic epoxy compounds examples include 3,4-epoxycyclohexenylmethyl-3′,4′-epoxycyclohexenecarboxylate, 3′,4′-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxycyclohexyloctyl-3,4-epoxycyclohexanecarboxylate, 2-(3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy)cyclohexane-m-dioxane, bis(3 ,4-epoxycyclohexylmethyl)adipate, vinylcyclohexene dioxide, bis(3,4-epoxy-6-methylcyclohexylmethyl)adipate, 3,4-epoxy-6-methylcyclohexyl-3,4-epoxy-6-methyl Cyclohexane carboxylate, methylenebis(3,4-epoxy
  • alicyclic epoxy compound commercial products such as Celoxide 2021P, EHPE3150, EHPE3150CE, Epolead GT401 (trade name, manufactured by Daicel Corporation) may be used.
  • Celoxide 2021P EHPE3150
  • EHPE3150CE Epolead GT401
  • 1,2-epoxy-4-(2-oxiranyl of 2,2-bis(hydroxymethyl)-1-butanol is preferred from the viewpoint of improving the adhesiveness of the cured film to members.
  • cyclohexane adducts are preferred.
  • trimethylolpropane polyglycidyl ether examples include trimethylolpropane diglycidyl ether, trimethylolpropane triglycidyl ether, and mixtures thereof.
  • a commercial product such as EX-321L (trade name, manufactured by Nagase ChemteX Corporation) may be used.
  • the melamine-based curing agent is melamine or its derivative.
  • melamine curing agents include those exemplified as the melamine compounds.
  • the oxazoline-based curing agent is a crosslinkable oxazoline compound having two or more oxazoline groups in one molecule.
  • oxazoline curing agents include oxazoline group-containing polymers such as polymers of oxazoline group-containing monomers and copolymers of oxazoline group-containing monomers and other monomers.
  • commercially available products such as "Epocross” series (trade name, manufactured by Nippon Shokubai Co., Ltd.) may be used.
  • Examples of the oxazoline group-containing monomer include 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, and 2-isopropenyl-2-oxazoline. , 2-isopropenyl-4-methyl-2-oxazoline, 2-isopropenyl-5-ethyl-2-oxazoline, 2-isopropenyl-2-oxazoline, 2-isopropenyl-4,4-dimethyl-2-oxazoline are mentioned.
  • One of these oxazoline group-containing monomers may be used alone, or two or more may be used in combination.
  • alkyl (meth)acrylates alkyl group having about 1 to 14 carbon atoms
  • Unsaturated carboxylic acids such as (sodium salts, potassium salts, ammonium salts, tertiary amine salts, etc.); unsaturated nitriles such as acrylonitrile and methacrylonitrile; , N-dialkyl (meth)acrylamide, (alkyl group: methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, 2-ethylhexyl group, cyclohexyl group, etc.), etc.
  • unsaturated carboxylic acids such as (sodium salts, potassium salts, ammonium salts, tertiary amine salts, etc.); unsaturated nitriles such as acrylonitrile and methacrylonitrile; , N-dialkyl (meth)acrylamide, (alkyl group: methyl group, ethyl group, n
  • vinyl esters such as vinyl acetate and vinyl propionate; vinyl ethers such as methyl vinyl ether and ethyl vinyl ether; ⁇ -olefins such as ethylene and propylene; Halogen ⁇ , ⁇ -unsaturated monomers; ⁇ , ⁇ -unsaturated aromatic monomers such as styrene and ⁇ -methylstyrene. These may be used individually by 1 type, or may use 2 or more types together.
  • the active energy ray-curable component contains a compound having a radically polymerizable carbon-carbon double bond, and is polymerized and cured in a short time by an active energy ray such as ultraviolet rays. It has the characteristic of Such a compound having a radically polymerizable carbon-carbon double bond has two or more radically polymerizable carbon-carbon double bonds in one molecule from the viewpoint of facilitating the formation of a three-dimensional network structure. It is preferably a compound having
  • Examples of the compound having a radically polymerizable carbon-carbon double bond include, for example, polyol, polyisocyanate, and polyurethane (meth)acrylate-based oligomer which is a reaction product of raw materials containing hydroxyalkyl (meth)acrylate; Reactive monomer; polyether, polyester, polycarbonate, poly(meth)acrylate, polybutadiene or butadiene-acrylonitrile copolymer compound having an acrylic group; polyether, polyester, polycarbonate, poly(meth)acrylate, polybutadiene or butadiene - A compound that is an acrylonitrile copolymer and has an allyl group; a compound that has a maleimide group;
  • Polyurethane (meth)acrylate Oligomer is a reaction product of raw materials including polyol, polyisocyanate, and hydroxyalkyl (meth)acrylate. Such polyurethane (meth)acrylate oligomers may be used alone or in combination of two or more. Each component of the raw material for the polyurethane (meth)acrylate oligomer will be described below.
  • polyol The polyol may be appropriately selected and used from among the polyols exemplified as those used in the urethane resin as the thermosetting component. Preferred polyols may also be the same as above.
  • polyisocyanate The polyisocyanate may be appropriately selected and used from the polyisocyanates exemplified as those used in the urethane resin as the thermosetting component. Preferred polyisocyanates may also be the same as above
  • hydroxyalkyl (meth)acrylate is a compound having one or more hydroxyl groups, one or more (meth)acryloyl groups and a hydrocarbon group having 1 to 30 carbon atoms. Hydroxyalkyl (meth)acrylates may be used alone or in combination of two or more.
  • hydroxyalkyl (meth)acrylates examples include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, cyclohexanedi Methanol mono(meth)acrylate, addition reaction product of 2-hydroxyethyl (meth)acrylate and caprolactone, addition reaction product of 4-hydroxybutyl (meth)acrylate and caprolactone, addition of glycidyl ether and (meth)acrylic acid
  • Examples include reactants, mono(meth)acrylate forms of glycol, pentaerythritol tri(meth)acrylate, and dipentaerythritol penta(meth)acrylate.
  • a hydroxyalkyl (meth)acrylate having an alkylene group having 2 to 4 carbon atoms between the hydroxyl group is particularly preferred.
  • the above polyurethane (meth)acrylate oligomer may further contain other components in its starting material.
  • Such other components include, for example, chain extenders.
  • the chain extender may be appropriately selected from the chain extenders exemplified as those used in the urethane resin as the thermosetting component.
  • the amount of all isocyanate groups in the polyurethane (meth)acrylate oligomer and the amount of all functional groups that react with isocyanate groups such as hydroxyl groups and amino groups are usually theoretically equimolar and expressed in mol%.
  • the amounts of the polyisocyanate, polyol, hydroxyalkyl (meth)acrylate, and other raw material compounds used in the polyurethane (meth)acrylate-based oligomer are determined by the total amount of isocyanate groups in the polyurethane (meth)acrylate-based oligomer and the reaction therewith.
  • the amount of all the functional groups is an equimolar amount, or an amount that is 50 mol % or more and 200 mol % or less in terms of mol % of the functional groups to the isocyanate group.
  • the amount of hydroxyalkyl (meth)acrylate used is reacted with a hydroxyalkyl (meth)acrylate, a polyol compound having two or more hydroxyl groups, and an isocyanate such as a chain extender.
  • a hydroxyalkyl (meth)acrylate a polyol compound having two or more hydroxyl groups
  • an isocyanate such as a chain extender.
  • 10 mol% or more preferably 15 mol% or more, more preferably 25 mol% or more
  • 70 mol% or less preferably 50 mol% or less
  • the amount of the polyol used relative to the total amount of the compound including the polyol and the chain extender improves the liquid stability. Therefore, it is preferably 70 mol % or more, more preferably 80 mol % or more, still more preferably 90 mol % or more, and particularly preferably 95 mol % or more.
  • the polyurethane (meth)acrylate-based oligomer can be produced by subjecting the polyisocyanate to addition reaction of the polyol and the hydroxyalkyl (meth)acrylate.
  • the polyurethane (meth)acrylate oligomer can be produced by subjecting the polyisocyanate to an addition reaction with the other raw material compounds described above.
  • addition reactions can be carried out by any known method. Examples of such methods include the following methods (i) to (iii).
  • the polyisocyanate and the hydroxyalkyl (meth)acrylate are first reacted to synthesize a urethane (meth)acrylate prepolymer having both a (meth)acryloyl group and an isocyanate group in the molecule; A method of reacting the prepolymer with other raw material components.
  • the urethane prepolymer is formed by the urethanization reaction of the polyisocyanate and the polyol, and the polyurethane (meth)acrylate oligomer is a urethane compound having an isocyanate group at its end. Since it has a structure obtained by urethanizing the prepolymer and the hydroxyalkyl (meth)acrylate, the molecular weight can be controlled and acryloyl groups can be introduced at both ends. From such a point of view, the method (i) is preferable.
  • a solvent can be used to adjust the viscosity during the production of the polyurethane (meth)acrylate oligomer.
  • Solvents may be used alone or in combination of two or more, and any known solvent can be used. Examples of such solvents include aliphatic hydrocarbon solvents such as hexane, cyclohexane, methylcyclohexane, ethylcyclohexane, heptane, nonane, octane, isooctane, and decane; aromatic hydrocarbon solvents such as benzene, toluene, xylene, cumene, and ethylbenzene; hydrogen; ester solvents such as ethyl acetate and butyl acetate; ether solvents such as diethyl ether, diisopropyl ether and methyl-tert-butyl ether; ketone solvents such as cyclohexanone, methyl ethy
  • the solvent can usually be used in an amount of 300 parts by mass or less per 100 parts by mass of the active energy ray-curable polymer composition.
  • the reaction temperature is usually 20° C. or higher (preferably 40° C. or higher, more preferably 60° C. or higher) from the viewpoint of increasing the reaction rate and improving the production efficiency. be. Moreover, the reaction temperature is usually 120° C. or lower (preferably 100° C. or lower) from the viewpoint that side reactions such as allophanate-forming reactions are unlikely to occur.
  • the reaction liquid contains a solvent
  • the temperature is preferably below the boiling point of the solvent, and when (meth)acrylate is contained, the temperature is preferably 70°C or less from the viewpoint of preventing the reaction of the (meth)acryloyl group.
  • the reaction time is usually about 5 to 20 hours.
  • the addition reaction catalyst used in the production of the polyurethane (meth)acrylate oligomer can be selected from the range in which the effect of the present invention can be obtained.
  • ate bisma tris(2-ethylhexanoate), diisopropoxytitanium bis(acetylacetonate), titanium tetra(acetylacetonate), dioctanoxytitanium dioctanate, diisopropoxytitanium bis(ethylacetoacetate), etc. and known urethane polymerization catalysts represented by
  • the addition reaction catalyst may be used alone or in combination of two or more.
  • bismath tris(2-ethylhexanoate) is preferred from the viewpoint of environmental adaptability, catalytic activity and storage stability.
  • a polymerization inhibitor When producing a polyurethane (meth)acrylate oligomer, if the reaction solution contains (meth)acryloyl groups, a polymerization inhibitor can be used in combination.
  • polymerization inhibitors include phenols such as hydroquinone, hydroquinone monoethyl ether, and dibutylhydroxytoluene; amines such as phenothiazine and diphenylamine; dibutyldithiocarbamic acid; copper salts such as copper; and manganese salts such as manganese acetate. , nitro compounds, nitroso compounds and the like.
  • a polymerization inhibitor may be used individually by 1 type, or may use 2 or more types together. Among these polymerization inhibitors, phenols are preferred.
  • each raw material component is substantially the same (preferably the same) as the composition of the polyurethane (meth)acrylate oligomer described above.
  • active energy ray-reactive monomers include aromatic vinyl-based monomers, vinyl ester monomers, vinyl ethers, allyl compounds, (meth)acrylamides, and (Meth)acrylates, specifically, for example, aromatic vinyl monomers such as styrene, ⁇ -methylstyrene, ⁇ -chlorostyrene, vinyltoluene, divinylbenzene; vinyl acetate, vinyl butyrate, N- vinyl ester monomers such as vinylformamide, N-vinylacetamide, N-vinyl-2-pyrrolidone, N-vinylcaprolactam and divinyl adipate; vinyl ethers such as ethyl vinyl ether and phenyl vinyl ether; diallyl phthalate, trimethylolpropane diallyl ether, Allyl compounds such as allyl glycidyl ether; acrylamide, N,N-dimethylacrylamide, N,
  • (1-2-5) Compound having a maleimide group
  • the compound having a maleimide group is also appropriately selected from compounds exemplified as compounds having a radically polymerizable carbon-carbon double bond that is a thermosetting component. It may be selected and used. Preferable ones may be the same as above.
  • one of these compounds having a radically polymerizable carbon-carbon double bond may be used alone, or two or more thereof may be used in combination.
  • Preferred active energy ray-curing component provides a cured film with high hardness, excellent flexibility, and good adhesion to members (structures), and can be used in a wide range of compositions.
  • a polyurethane (meth)acrylate oligomer a compound having an acrylic group, a compound having an allyl group, and a compound having a maleimide group, and an active energy ray and a reactive monomer are preferred.
  • one or more of a polyurethane (meth)acrylate oligomer, a compound having an acrylic group, a compound having an allyl group, and a compound having a maleimide group is added to the entire component. It is preferably contained at a ratio of 1% by mass or more and 45% by mass or less, and preferably contains an active energy ray-reactive monomer at a ratio of 55% by mass or more and 99% by mass or less.
  • Active energy ray polymerization initiator In the antibacterial/antiviral agent composition, it is mainly necessary to improve the initiation efficiency of the polymerization reaction that proceeds when irradiated with active energy rays such as ultraviolet rays and electron beams. For the purpose, it is preferable that an active energy ray polymerization initiator is further included.
  • an active energy ray polymerization initiator a photoradical polymerization initiator which is a compound having a property of generating radicals by light is generally used, and any known photoradical polymerization initiator can be used.
  • the polymerization initiator may be used alone or in combination of two or more.
  • photoradical polymerization initiators include benzophenone, 2,4,6-trimethylbenzophenone, 4,4-bis(diethylamino)benzophenone, 4-phenylbenzophenone, methylorthobenzoylbenzoate, thioxanthone, diethylthioxanthone, isopropylthioxanthone, chloro Thioxanthone, 2-ethylanthraquinone, t-butylanthraquinone, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, 1-hydroxycyclohexylphenylketone, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, methylbenzoylformate, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one
  • benzophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexylphenyl ketone, 2 are preferred from the viewpoint that the curing speed is fast and the crosslink density can be sufficiently increased.
  • 4,6-trimethylbenzoyldiphenylphosphine oxide, and 2-hydroxy-1-[4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]-phenyl]-2-methyl-propane-1 -ones are preferred
  • 1-hydroxycyclohexylphenyl ketone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, and 2-hydroxy-1-[4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl ]-Phenyl]-2-methyl-propan-1-one is more preferred.
  • the photocationic polymerization initiator is used as a polymerization initiator together with the photoradical polymerization initiator.
  • agents may be included. Any known photocationic polymerization initiator can be used.
  • the content of these photopolymerization initiators is preferably 10 parts by mass or less with respect to a total of 100 parts by mass of active energy ray-reactive components, from the viewpoint that deterioration of mechanical strength due to decomposition products of the initiator is unlikely to occur. , 5 parts by mass or less is more preferable.
  • the photoradical polymerization initiator and photosensitizer may be used in combination.
  • a photosensitizer can be used for the same purpose as the polymerization initiator.
  • the photosensitizer may be used alone or in combination of two or more, and any known photosensitizer can be used. Examples of such photosensitizers include ethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, amyl 4-dimethylaminobenzoate, and 4-dimethylaminoacetophenone.
  • the content of the photosensitizer is preferably 10 parts by mass or less with respect to a total of 100 parts by mass of the active energy ray-reactive components, from the viewpoint that a decrease in mechanical strength due to a decrease in cross-linking density is unlikely to occur. 5 parts by mass or less is more preferable.
  • additives can be used singly or in combination of two or more.
  • Such other additives include, for example, antioxidants (e.g., 2,6-dibutyl-4-methylphenol (BHT), "CYANOX1790” manufactured by Sun Chemical Co., Ltd., "IRGANOX245" manufactured by BASF Japan Ltd.
  • antioxidants e.g., 2,6-dibutyl-4-methylphenol (BHT)
  • CYANOX1790 manufactured by Sun Chemical Co., Ltd.
  • IRGANOX245" manufactured by BASF Japan Ltd.
  • UV absorbers e.g., BASF Japan Co., Ltd., "TINUVIN328" and "TINUVIN234", etc.
  • silicone compounds e.g., dimethylsiloxane polyoxy alkylene copolymers, etc.
  • additive and reactive flame retardants e.g., red phosphorus, organic phosphorus compounds, phosphorus- and halogen-containing organic compounds, bromine- or chlorine-containing organic compounds, ammonium polyphosphate, aluminum hydroxide, antimony oxide, etc.
  • pigments e.g., titanium dioxide, etc.
  • dyes e.g., coloring agents (e.g., carbon black, etc.); hydrolysis inhibitors (e.g., carbodiimide compounds, etc.); Calcium, mica, zinc oxide, titanium oxide, mica, talc
  • the content of such other additives is preferably 10 parts by mass or less, and 5 parts by mass with respect to 100 parts by mass of the curing component, from the viewpoint that a decrease in mechanical strength due to a decrease in crosslink density is unlikely to occur.
  • the following are more preferred.
  • the content of the above mono/diester or salt thereof is not particularly limited, but it is said that there is little decrease in the hardness of the cured film and excellent antiviral properties can be obtained. From the viewpoint, it is preferably 0.1 to 50 parts by mass, more preferably 0.2 to 30 parts by mass, and 0.5 to 20 parts by mass with respect to 100 parts by mass of the curing component. The following are particularly preferred.
  • a solvent can be added to the antibacterial/antiviral agent composition for the purpose of adjusting the viscosity, depending on the coating method used to form the coating film.
  • Solvents may be used alone or in combination of two or more, and any known solvent can be used. Examples of such solvents include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; alcohols such as isopropanol and isobutanol; ethers such as dioxane and tetrahydrofuran; hydrocarbons; aromatic hydrocarbons such as toluene and xylene; esters such as ethyl acetate and butyl acetate; halogenated hydrocarbons such as chlorobenzene, trichlene and perchlene; Aprotic polar solvents such as 2-pyrrolidone, dimethylformamide and dimethylacetamide are preferred.
  • the solvent can usually be used in an amount of 500 parts by mass or less with respect to 100 parts by mass of the curing component.
  • concentration of the mono/diester or salt thereof is not particularly limited, but is 0.01% by mass or more and 30% by mass based on the total composition. The following is preferable, 0.02 mass % or more and 20 mass % or less is more preferable, and 0.04 mass % or more and 10 mass % or less is particularly preferable.
  • the viscosity of the antibacterial/antiviral agent composition can be appropriately adjusted according to its application and usage mode.
  • the viscosity measured at 25° C. with (rotor 1°34′ ⁇ R24) is preferably 10 mPa s or more, more preferably 100 mPa s or more, and 100,000 mPa s or less. , and more preferably 50,000 mPa ⁇ s or less.
  • the adjustment of the viscosity can be appropriately adjusted depending on the content of the curing component, the type and content of other components, and the like.
  • the antibacterial/antiviral agent composition can be produced by mixing the mono/diester or its salt, the curing component, and, if necessary, a curing agent, other additives, and a solvent.
  • the mixing method is not particularly limited, and includes conventionally known mixing and dispersing methods. Homomixer, disper, double roll, triple roll, bead mill, ball mill, sand mill, pebble mill, tron mill, sand grinder, segvariator, planetary stirrer, high speed impeller disperser, high speed stone mill, high speed impact mill, kneader , a homogenizer, an ultrasonic disperser, or the like may be used.
  • the method of coating the antibacterial/antiviral agent composition includes the bar coater method, applicator method, curtain flow coater method, roll coater method, spray method, gravure coater method, comma coater method, reverse roll coater method, lip coater method, Known methods such as a die coater method, a slot die coater method, an air knife coater method and a dip coater method can be applied, and among them, a bar coater method and a gravure coater method are preferred.
  • the antibacterial/antiviral agent composition according to the present embodiment can be used as a treatment agent for imparting at least antiviral properties to various structures. For example, by bringing the antibacterial/antiviral agent composition according to the present embodiment into contact with various structures, at least antiviral properties can be imparted to the structures.
  • the antibacterial/antiviral agent composition is used in a liquid form such as a treatment liquid or paint.
  • the surface of various other structures may be wiped with the various structures to which the antibacterial/antiviral agent composition according to the present embodiment is attached.
  • the antibacterial/antiviral agent composition according to the present embodiment can be used to disinfect fingers, utensils, and the like.
  • a spray bottle may be filled with the antibacterial/antiviral agent composition and used.
  • the antibacterial/antiviral agent composition according to the present embodiment can be used to impart antiviral properties to various structures.
  • the antibacterial/antiviral structure according to the present embodiment includes a base material and the above antibacterial/antiviral agent composition.
  • the method for producing an antibacterial/antiviral structure according to this embodiment includes bringing the above antibacterial/antiviral agent composition into contact with a substrate.
  • substrates can be used to construct the structure.
  • the substrate may be plastic, glass, metal, wood, paint film, synthetic leather, or the like.
  • the shape of the substrate is not particularly limited, and may be appropriately determined according to the use of the structure.
  • the amount of the antibacterial/antiviral agent composition adhered to the substrate is particularly limited. not something.
  • the amount of the antibacterial/antiviral agent (mono/diester or salt thereof) attached to the substrate may be 0.01 g/m 2 or more, or 0.02 g/m 2 or more, and 20 g/m 2 or less, or 10 g. /m 2 or less.
  • the amount of the antibacterial/antiviral agent attached is 0.01 g/m 2 or more, a higher antiviral effect can be obtained.
  • the adhesion amount of the water-based polyurethane resin to the substrate may be 0.01 g/m 2 or more, or 0.06 g/m 2 or more, and may be 20 g/m 2 or more. m 2 or less, or 10 g/m 2 or less.
  • the adhesion amount of the water-based polyurethane resin is 0.01 g/m 2 or more, the durability of the antiviral agent is further improved.
  • the adhesion amount of the water-based polyurethane resin is 20 g/m 2 or less, the texture can be further softened.
  • the antibacterial/antiviral structure may have additional additives.
  • additives include coloring agents, antioxidants, light stabilizers, ultraviolet absorbers, flame retardants, softeners, cross-linking agents, and other thermoplastic resins.
  • the antibacterial/antiviral agent composition When the antibacterial/antiviral agent composition according to the present embodiment is used to treat a substrate in an aqueous system, the antibacterial/antiviral agent composition contains a mono/diester or a salt thereof and an aqueous resin as described above.
  • the antibacterial/antiviral agent composition can be attached to the substrate by bringing the treatment liquid into contact with the substrate.
  • a treatment liquid for imparting antiviral properties to the substrate is obtained. be able to.
  • the concentration of the mono/diester or its salt in the treatment liquid is, for example, 0.001% by mass or more, 0.002% by mass or more, 0.01% by mass or more, or 0.02% by mass. It may be at least 5% by mass, or at most 4% by mass. When it is 0.001% by mass or more and 4% by mass or less, the balance between performance and cost is excellent.
  • An aqueous solvent water or a mixture of water and an organic solvent
  • organic solvents examples include ethanol, propanol, acetone, and acetonitrile.
  • the concentration of the water-based resin in the treatment liquid may be, for example, 0.001% by mass or more, 0.005% by mass or more, or 0.1% by mass or more, and 20% by mass or less, or It may be 10% by mass or less. When it is 0.001% by mass or more and 20% by mass or less, the balance between performance and cost is excellent.
  • the above mono/diester or salt thereof, water-based polyurethane resin, etc. are diluted with a water-based solvent to a predetermined concentration to prepare a treatment liquid. Subsequently, the treatment liquid is brought into contact with the substrate to produce a structure having antiviral properties.
  • Examples of methods for bringing the treatment liquid into contact with the substrate include a coating method and a spray method.
  • the antibacterial/antiviral agent composition is adjusted to have an appropriate viscosity, and the composition (treatment liquid) is coated on the substrate and then dried to remove the mono/diester or its salt. It can be immobilized on a substrate.
  • the coating method is not particularly limited, and examples thereof include gravure roll processing, spray processing, roll coater processing, jet printing processing, transfer printing processing, screen printing processing and the like.
  • the base material After treating the base material with a treatment liquid containing a mono/diester or its salt, and a water-based polyurethane resin, etc., it may be washed as necessary and dried naturally or dried by heating.
  • heat drying devices such as loop dryers, net dryers, ovens and heat setters can be used.
  • the drying/heating temperature of the substrate to which the treatment liquid containing the mono/diester or its salt and the water-based polyurethane resin is applied can be 80 to 190°C, preferably 100 to 160°C. Treatment times may be 30 seconds or longer, or 1 minute or longer, 10 minutes or shorter, or 30 minutes or shorter.
  • the above antibacterial/antiviral agent composition may be of a two-liquid type. That is, a first liquid containing a water-based polyurethane resin and a second liquid containing a mono/diester or a salt thereof are prepared, and after one liquid is brought into contact with the substrate, the other liquid is brought into contact. may produce an antiviral structure. Also in this case, the antibacterial/antiviral agent composition can be adhered to the surface of the substrate.
  • Non-aqueous treatment When the antibacterial/antiviral agent composition according to the present embodiment is used to treat a substrate in a non-aqueous system, the treated structure has a cured film on its surface. good too. A cured film and a structure including the cured film will be described below.
  • the cured film is a cured product of the above antibacterial/antiviral agent composition, and in addition to antiviral properties, it can have, for example, immediate antiviral effects and transparency.
  • a cured film can be formed by subjecting a coating film made of the above antibacterial/antiviral agent composition to a curing treatment after washing as necessary.
  • the curing treatment may be selected depending on the curing component, and examples thereof include heat curing treatment by natural drying or heat drying, and curing treatment by active energy rays.
  • Heat drying can be performed using a known heat drying device such as a loop dryer, a net dryer, an oven, or a heat setter.
  • the treatment temperature in natural drying or heat drying can be appropriately set according to the thermosetting component contained in the antibacterial/antiviral agent composition, but is preferably 5 to 190°C, more preferably 10 to 160°C. .
  • the treatment time for natural drying or heat drying can be appropriately set according to the thermosetting component contained in the antibacterial/antiviral agent composition, but is preferably 30 seconds to 24 hours, and 1 to 30 minutes. is more preferred.
  • the thickness of the cured film can be appropriately determined according to the intended use, but is preferably 1 ⁇ m or more, more preferably 3 ⁇ m or more, particularly preferably 5 ⁇ m or more, and preferably 200 ⁇ m or less, and 100 ⁇ m or less. is more preferable, 50 ⁇ m or less is particularly preferable, and 20 ⁇ m or less is most preferable. If the thickness of the cured film is less than the lower limit, the design and functionality after curing may be insufficient. may be.
  • the structure provided with the above cured film includes a substrate and a layer made of the cured film disposed on the surface of the substrate. This structure has excellent antiviral properties. Moreover, when the base material has transparency, the transparency is also excellent.
  • the layer composed of the cured film may be directly disposed on the surface of the substrate, and between the layer composed of the cured film and the substrate, other than the cured film and the substrate other layers may be further arranged.
  • a layer other than the cured film and the base material may be further arranged outside the laminate composed of the layer composed of the cured film and the base material.
  • a method for producing a structure provided with such a cured film for example, (1) all layers including a coating film made of an antibacterial/antiviral agent composition are laminated on the base material in an uncured state. , and a method of curing by natural drying or heat drying after washing as necessary.
  • the method of laminating a plurality of layers in an uncured state is not particularly limited. Known coating methods such as a simultaneous multi-layer coating method in which two or more layers are simultaneously formed in an uncured state using a slit can be used.
  • the structure comprises a layer made of the cured film and other layers (that is, when comprising a plurality of layers)
  • an uncured lower layer is placed on the base material.
  • the method (1) is preferably adopted from the viewpoint of improving the interlayer adhesion.
  • the amount of the antibacterial/antiviral agent composition attached to the base material when producing a structure having a cured film is not particularly limited, but the hardness of the cured film is less reduced, and excellent antiviral properties are obtained. From the viewpoint of obtaining the antibacterial/antiviral agent (mono/diester or its salt) on the substrate, the amount is preferably 0.01 g/m 2 or more and 50 g/m 2 or less, and is preferably 0.02 g/m A more preferable amount is 2 or more and 25 g/m 2 or less.
  • the adhesion amount of the thermosetting component to the substrate is 0.05 g/m2 or more and 100 g/m2. It is preferably m 2 or less, more preferably 0.1 g/m 2 or more and 50 g/m 2 or less.
  • active energy rays examples include infrared rays, visible rays, ultraviolet rays, X-rays, electron beams, ⁇ rays, ⁇ rays, and ⁇ rays. From the viewpoint of equipment cost and productivity, it is preferable to use electron beams or ultraviolet rays. Ar laser, He-Cd laser, solid-state laser, xenon lamp, high-frequency induction mercury lamp, sunlight, etc. are suitable. When curing by electron beam irradiation, the irradiation dose is preferably 1 to 10 Mrad. In the case of ultraviolet irradiation, 50 to 1,000 mJ/cm 2 is preferable.
  • the atmosphere during curing may be air or an inert gas such as nitrogen or argon. Alternatively, irradiation may be performed in a closed space between the film or glass and the metal mold.
  • the thickness of the film cured by the active energy ray can be appropriately determined depending on the intended use, but is preferably 1 ⁇ m or more, more preferably 3 ⁇ m or more, particularly preferably 5 ⁇ m or more, and 200 ⁇ m or less. It is preferably 100 ⁇ m or less, particularly preferably 50 ⁇ m or less, and most preferably 20 ⁇ m or less. If the thickness of the cured film is less than the lower limit, the design and functionality after curing may be insufficient. may be.
  • the structure comprises a substrate and a layer composed of the cured film arranged on the surface of the substrate.
  • This structure has excellent antiviral and immediate antiviral properties. Moreover, when the member has transparency, the transparency is also excellent.
  • the layer composed of the cured film may be directly disposed on the surface of the substrate, and between the layer composed of the cured film and the substrate, other than the cured film and the substrate other layers may be further arranged.
  • a layer other than the cured film and the base material may be further arranged outside the laminate composed of the layer composed of the cured film and the base material.
  • a method for producing a structure having a film cured by such an active energy ray for example, (1) all layers including a coating film made of the above antibacterial/antiviral agent composition are uncoated on the base material.
  • a method of curing by irradiating an active energy ray after lamination in a cured state can be mentioned.
  • the method of laminating a plurality of layers in an uncured state is not particularly limited.
  • Known coating methods such as a simultaneous multi-layer coating method in which two or more layers are simultaneously formed in an uncured state using a slit can be used.
  • the structure comprises a layer made of the cured film and other layers (that is, when comprising a plurality of layers)
  • an uncured lower layer is placed on the base material.
  • the upper layer After laminating in a state and curing or semi-curing by irradiation with active energy rays, the upper layer is laminated on it in an uncured state and cured by irradiation with active energy rays again;
  • a method may also be adopted in which each layer is formed in an uncured or semi-cured state on the mold film or the base film, these layers are bonded together, and then cured by irradiation with active energy rays.
  • the method (1) is preferably adopted from the viewpoint of improving the interlayer adhesion.
  • the amount of the antibacterial/antiviral agent composition adhered to the base material when manufacturing a structure having a film cured by active energy rays is not particularly limited, but there is little decrease in the hardness of the cured film, and it is excellent.
  • the amount of the antibacterial/antiviral agent (mono/diester or salt thereof) attached to the member is preferably 0.01 g/m 2 or more and 20 g/m 2 or less. An amount of 02 g/m 2 or more and 10 g/m 2 or less is more preferable.
  • the adhesion amount of the active energy ray-curable component to the substrate is 0.05 g/m 2 or more and 50 g. /m 2 or less, more preferably 0.1 g/m 2 or more and 20 g/m 2 or less.
  • the structure may be used as various products.
  • the antibacterial/antiviral agent composition according to the present embodiment can be used in various forms. For example, it can be used by carrying it on products that may come into contact with viruses.
  • Examples of products that can carry the antibacterial/antiviral agent composition include textile products and products other than textile products (eg, breathable sheets, medical instruments, and interior materials such as wall materials).
  • An antibacterial/antiviral textile product will be described in detail below as an example of the structure.
  • the type of the fiber is not particularly limited, and may be a natural fiber or a chemical fiber.
  • fibers include natural fibers such as cotton, hemp, silk, and wool; semi-synthetic fibers such as rayon and acetate; synthetic fibers such as polyamide (nylon, etc.), polyester, polyurethane, and polypropylene; Blended fibers are mentioned.
  • Polyamides include nylon 6, nylon 6,6 and the like.
  • polyesters include polyethylene terephthalate, polytrimethylene terephthalate, and polylactic acid.
  • the fibers may be in the form of yarn, knitted fabric (including mixed knit), woven fabric (including mixed weave), non-woven fabric, carpet, paper, wood, and the like.
  • the fibers may be dyed.
  • the fibers may have undergone some modification treatment on their surface.
  • the amount of the antibacterial/antiviral composition adhered to the fiber is not particularly limited.
  • the amount of the antibacterial/antiviral agent (mono/diester or its salt) is preferably 0.001 to 10 parts by mass per 100 parts by mass of the fiber. Below the lower limit, the antiviral effect tends to decrease. On the other hand, when the upper limit is exceeded, the antiviral effect tends to saturate.
  • the antibacterial/antiviral agent composition may contain water, or may contain an organic solvent and water.
  • the antibacterial/antiviral agent composition may also contain an acid component, an alkaline component, a chelating agent, a preservative, a melamine resin, a glyoxal resin, an isocyanate compound, an antifoaming agent, a water repellent, a softening agent, and the like.
  • the method for producing antibacterial/antiviral textile products includes contacting the antibacterial/antiviral agent composition with the antibacterial/antiviral agent composition. .
  • the method of bringing the antibacterial/antiviral agent composition into contact with the fiber is not particularly limited. For example, by bringing an object into contact with a treatment liquid (which may be a solution or a dispersion) containing an antibacterial/antiviral agent composition, the object is treated with the antibacterial/antiviral agent composition. You can attach things.
  • the timing of performing the treatment with the treatment liquid is not particularly limited.
  • the treatment liquid may contain, for example, the above mono/diester or a salt thereof. Moreover, the treatment liquid may contain other components such as an acid component, an alkali component, a surfactant, and a chelating agent.
  • the pH of the treatment liquid is not particularly limited, but may be, for example, 2 or more and 8 or less. If you want to improve the durability, use melamine resin, glyoxal resin, isocyanate compound, etc. in combination in the above-mentioned process of treating the object with the treatment liquid containing the antibacterial / antiviral agent composition.
  • the object can also be treated by a method that includes applying it to the object and heating it.
  • Specific examples of the method of treating the fiber, which is the object, with the treatment liquid include padding treatment, immersion treatment, and coating treatment (for example, at least one treatment selected from spray treatment, inkjet treatment, bubble treatment, coating treatment, etc.). There may be) and the like.
  • the concentration of the treatment liquid at this time and the treatment conditions such as heat treatment after application may be appropriately adjusted in consideration of various conditions such as the purpose and performance.
  • washing treatment such as washing with water may be performed in order to remove excess antibacterial/antiviral agent.
  • a drying treatment may be performed to remove the water after the treatment liquid is adhered to the object.
  • the drying method is not particularly limited, and may be either a dry heat method or a wet heat method.
  • the drying temperature and drying time are not particularly limited, either. For example, drying may be performed at room temperature to 200° C. for 10 seconds to several days. 20 seconds to 60 minutes at 40 to 130° C. is more preferable.
  • the antibacterial/antiviral agent composition according to the present embodiment can be used in various fields.
  • the fibers described above can be used in, for example, the following fields.
  • the antibacterial/antiviral agent composition according to the present embodiment can be widely used for elastomers, paints, adhesives, flooring materials, sealants, medical materials, artificial leather, coating agents, etc. In these applications, Various characteristics can be expressed. In particular, when the antibacterial/antiviral agent composition according to the present embodiment is used for applications such as artificial leather, synthetic leather, medical materials, flooring materials, and coating agents, in addition to antiviral properties, abrasion resistance and blocking resistance can be obtained. Because of its excellent toughness, it is possible to impart good surface properties such as being less likely to be scratched or the like and less likely to be deteriorated by friction.
  • the antibacterial/antiviral agent composition according to this embodiment can also be used as a thermoplastic elastomer.
  • a thermoplastic elastomer for example, it can be used for tubes and hoses, spiral tubes, fire hoses, etc. in pneumatic equipment used in the food and medical fields, coating equipment, analytical equipment, physical and chemical equipment, metering pumps, water treatment equipment, industrial robots, and the like.
  • it can be used as a belt such as a round belt, a V belt, a flat belt, etc. for various transmission mechanisms, spinning machines, packing machines, printing machines, and the like.
  • it can be used for heel tops and soles of footwear, couplings, packings, pole joints, bushes, gears, machine parts such as rolls, sporting goods, leisure goods, watch belts, and the like.
  • automotive parts such as oil stoppers, gearboxes, spacers, chassis parts, interior parts, and tire chain substitutes.
  • films such as keyboard films and films for automobiles, curled cords, cable sheaths, bellows, conveyor belts, flexible containers, binders, synthetic leathers, dipping products, adhesives and the like.
  • the antibacterial/antiviral agent composition according to this embodiment can be applied to wood products such as musical instruments, Buddhist altars, furniture, decorative plywood, and sporting goods. It can also be used for automobile repair.
  • the antibacterial/antiviral agent composition according to the present embodiment includes, for example, paints for plastic bumpers, strippable paints, coating agents for magnetic tapes, floor tiles, flooring materials, paper, overprint varnishes such as wood grain printed films, and wood. It can be applied to varnish, coil coat for high processing, optical fiber protective coating, solder resist, top coat for metal printing, base coat for vapor deposition, white coat for food cans, etc.
  • the antibacterial/antiviral agent composition according to this embodiment can be applied as an adhesive to food packaging, shoes, footwear, magnetic tape binders, decorative paper, wood, structural members, OCR materials inside liquid crystal panels, and the like.
  • the antibacterial/antiviral agent composition according to the present embodiment includes metal materials such as iron, copper, aluminum, ferrite, and plated steel sheets, and resins such as acrylic resins, polyester resins, ABS resins, polyamide resins, polycarbonate resins, and vinyl chloride resins.
  • resins such as acrylic resins, polyester resins, ABS resins, polyamide resins, polycarbonate resins, and vinyl chloride resins.
  • Inorganic materials such as materials, glass, and ceramics can be efficiently bonded.
  • the antibacterial/antiviral agent composition according to the present embodiment includes binders such as magnetic recording media, inks, castings, baked bricks, graft materials, microcapsules, granular fertilizers, granular pesticides, polymer cement mortar, resin mortar, rubber chip binders, It can be used for recycled foam, glass fiber sizing, etc.
  • binders such as magnetic recording media, inks, castings, baked bricks, graft materials, microcapsules, granular fertilizers, granular pesticides, polymer cement mortar, resin mortar, rubber chip binders, It can be used for recycled foam, glass fiber sizing, etc.
  • the antibacterial/antiviral agent composition according to the present embodiment can be used as a sealant/caulk for concrete rammed walls, induced joints, around sashes, wall-type PC joints, ALC joints, board joints, composite glass sealants, and heat-insulating sash sealants. , automotive sealants, etc.
  • the antibacterial/antiviral agent composition according to this embodiment can be used as a medical material, such as tubes, catheters, artificial hearts, artificial blood vessels, artificial valves, etc. as blood compatible materials, and catheters as disposable materials. , tubes, bags, surgical gloves, artificial kidney potting materials, etc.
  • the antibacterial/antiviral agent composition according to the present embodiment is used as a raw material for UV curable coatings, electron beam curable coatings, photosensitive resin compositions for flexographic printing plates, photocurable optical fiber coating compositions, and the like. be able to.
  • the antibacterial/antiviral agent composition when a water-based resin is used together with the above mono/diester or salt thereof, the antibacterial/antiviral agent composition is particularly suitable for leather (artificial leather, synthetic leather ) as an antiviral treatment agent.
  • a non-aqueous resin when used together with the above mono/diester or salt thereof, it can be used as a coating agent for flexible materials such as bendable films.
  • it can be effectively applied to electronic devices such as touch panels of mobile phones, monitors, tablets, etc., and optical devices such as spectacle lenses.
  • the technology of the present disclosure also has an aspect as a virus inactivating method using an antibacterial/antiviral agent composition.
  • the antibacterial/antiviral agent composition according to the present embodiment can be applied to doorknobs, bed rails, handrails, floor surfaces, walls, ceilings, drains, bathtubs, and sinks in hospital rooms, bathrooms, kitchens, toilets, etc. , toilet bowls, washstands, etc., and doorknobs, handrails, etc. in toilets, floors, walls, ceilings, drains, toilet bowls, washstands, etc. in each factory such as food factories, and surfaces of various manufacturing equipment. It can also be used when performing an activation treatment. In particular, it is useful for use as a frequently touched finger surface in medical institutions such as hospitals and food factories.
  • the antibacterial/antiviral agent composition includes a chelating agent, a rust inhibitor, an antifoaming agent, an antiseptic, a surfactant, an antioxidant, a coloring agent, a deodorant, a fragrance, an acid component, and an alkali component. etc. can be blended.
  • the antibacterial/antiviral agent composition may be used as it is, or the composition may be diluted with water and used as a treatment liquid.
  • water in this case tap water, well water, ion-exchanged water, or distilled water can be suitably used.
  • the concentration of the mono/diester or its salt in the antibacterial/antiviral agent composition can be appropriately adjusted depending on the application.
  • the virus inactivation method using the antibacterial/antiviral agent composition according to the present embodiment includes the step of contacting the composition with an object such as a device to be subjected to virus inactivation treatment. It is not particularly limited. Spraying the treatment liquid on the surface to be treated, equipment, etc. using a device equipped with a nozzle, etc., simply moistening or immersing the surface to be treated, equipment, etc. in the treatment liquid, wiping, etc. Examples include impregnating a substrate and using it as a cleaning article, circulating the inside of equipment, and the like.
  • the temperature during the treatment is not particularly limited, but from the viewpoint of antiviral properties, washing properties, and economy, it is preferably 10 to 60°C, more preferably 10 to 30°C.
  • the processing time varies depending on the shape/size of the object, the processing method, and the processing conditions, and is not particularly limited.
  • Antiviral treatment for textiles 1.1 Preparation of solutions of compounds A to C and E to K To an alkyl phosphate ester prepared from an alcohol shown in Table 1 below and phosphoric anhydride (diphosphorus pentoxide), water and A neutralized salt shown in Table 1 below was added to adjust the alkyl phosphate salt to 15% by mass. When a uniform liquid was not obtained, an organic solvent was added as appropriate to adjust the amount of the alkyl phosphate to 15% by mass.
  • the types of alkyl groups and salts are shown in Table 1 below.
  • Example 16 A 100% wool fabric (basis weight: 100 g/m 2 ) is immersed in the above treatment liquid, treated at a squeezing rate of 80%, and then heat-treated at 120 ° C. for 1 minute to have antiviral properties. A textile product was obtained.
  • the antiviral activity value was measured according to JIS L1922 (2016) to evaluate the antiviral performance of the textile product.
  • influenza A virus H3N2 ATCC VR-1679 was used.
  • Antiviral activity value was evaluated as log(Va)-log(Vc).
  • log(Va) is the common logarithm of the viral infectivity titer recovered from the unprocessed sample immediately after virus inoculation
  • log(Vc) is the common logarithm of the viral infectivity titer recovered from the processed sample after 2 hours of virus action. .
  • the higher the activity value the better the antiviral properties.
  • an antiviral activity value of 2.0 or more is considered to be effective, but viruses are reduced even if the activity value is 2.0 or less. In this example, it is determined that even an activity value of 1.4 has an antiviral effect.
  • the antibacterial activity value was measured by JIS L1902 (2015) quantitative test (8.2 bacterial liquid absorption method) to evaluate the antibacterial performance of the textile product. Klebsiella pneumoniae NBRC13277 was used as the bacterium used. The higher the activity value, the better the antibacterial properties. In this example, the antibacterial activity was judged to be good when the antibacterial activity value was 2.0 or more.
  • Water-based polyurethane resins used in this example are as follows. The following water-based polyurethane resins were obtained by preparing an emulsified dispersion (solvent: water) having a concentration of 35% by mass of the polyurethane resin, and then standing the emulsified dispersion at atmospheric pressure at 20°C for 12 hours. Separation and sedimentation were not observed even when placed.
  • solvent water
  • 1,6-hexanediol polycarbonate polyol molecular weight 1,000
  • DMPA dimethylolpropionic acid
  • 3 parts, 3.4 parts of 1,4-BD (butanediol), and 114.5 parts of methyl ethyl ketone as a solvent are weighed and mixed uniformly, and then 77.0 parts of HDI (hexamethylene diisocyanate) as a polyisocyanate is added. , and 80 ⁇ 5° C.
  • 7.3 parts of triethylamine was added at 60° C. to carry out a neutralization reaction.
  • 643.2 parts of water was gradually added and stirred to emulsify and disperse the terminal isocyanate group-containing urethane prepolymer.
  • a polyamine aqueous solution prepared by dissolving 9.2 parts of hydrazine monohydrate and 1.9 parts of diethylenetriamine in 33.1 parts of water was added, stirred at 40 ⁇ 5° C.
  • the monomer emulsion used above is a monomer mixture of 25 parts of methyl methacrylate and 75 parts of butyl acrylate, and sodium polyoxyethylene alkyl ether sulfate (manufactured by Kao Corporation, trade name: Latemul E-118B). 4 parts and 30 parts of ion-exchanged water were mixed and emulsified. In parallel with the dropping of the monomer emulsion, 4 parts of a 5% concentration ammonium persulfate aqueous solution was dropped. After completion of dropping, the mixture was aged at 80° C. for 4 hours, and then cooled to room temperature. Finally, the mixture was neutralized with aqueous ammonia and adjusted with water to obtain a water-based acrylic resin composition having a non-volatile content of 60%.
  • Antibacterial/Antiviral Agent Composition A solution of compound A or a solution of compound L, the water-based polyurethane resin composition, the water-based acrylic resin composition, other additives, etc., were prepared according to Table 3 below. were mixed at the mass ratio shown in , to obtain antibacterial/antiviral agent compositions according to Examples 1A, 2A and Comparative Example 1A.
  • the antiviral activity value was measured according to ISO21702:2019, and the antiviral performance of the leather-like laminate after the antibacterial/antiviral agent composition was fixed was evaluated.
  • influenza A virus H3N2 ATCC VR-1679 was used.
  • Antiviral activity value R (Ut-U0)-(At-U0).
  • U0 is the average common logarithm (PFU/cm 2 ) of the number of plaques recovered from the raw sample immediately after inoculation
  • Ut is the average common logarithm (PFU/cm 2 ) of the number of plaques recovered from the raw sample after 24 hours.
  • At is the mean common logarithm (PFU/cm 2 ) of the number of plaques recovered from the processed samples after 24 hours.
  • PFU/cm 2 the mean common logarithm
  • the antibacterial activity value was measured according to JIS Z2801:2010 to evaluate the antibacterial performance of the leather-like laminate after the antibacterial/antiviral agent composition was fixed.
  • Staphylococcus aureus NBRC12732 was used as the bacterium. The higher the activity value, the better the antibacterial properties. In this example, the antibacterial activity was judged to be good when the antibacterial activity value was 2.0 or more.
  • Antiviral spray 3.1 Preparation of spray composition As shown in Table 4 below, the spray compositions according to Example 1B and Comparative Example 1B consisted of a solution of compound A (isodecyl phosphate ester Na) and compound L ( A solution of dodecyl sulfate (Na) was prepared respectively.
  • the antiviral activity value was measured according to ISO21702:2019, and the antiviral performance of the leather-like laminate after the antiviral agent composition was fixed was evaluated.
  • influenza A virus H3N2 ATCC VR-1679 was used.
  • Antiviral activity value R (Ut-U0)-(At-U0).
  • U0 is the average common logarithm (PFU/cm 2 ) of the number of plaques recovered from the raw sample immediately after inoculation
  • Ut is the average common logarithm (PFU/cm 2 ) of the number of plaques recovered from the raw sample after 24 hours.
  • At is the mean common logarithm (PFU/cm 2 ) of the number of plaques recovered from the processed samples after 24 hours.
  • a bacterial solution was prepared as follows. (1) A given bacterium was cultured in a soybean-casein digest liquid medium at 37° C. for 24 hours. (2) After culturing, the number of bacteria was adjusted to 10 7 to 10 9 CFU/ml with pH 7.4 phosphate-buffered saline to prepare a bacterial solution.
  • Example 1B or Comparative Example 1B instead of 9.9 mL of the spray composition according to Example 1B or Comparative Example 1B, the same operation was performed using 9.9 mL of physiological saline as a control operation, and the number of surviving bacteria after the control operation and the number of surviving bacteria after contact with the composition of Example 1B or Comparative Example 1B was calculated as an index of sterilization performance, and a logarithmic difference of 3 or more was considered good.
  • Example 1B containing isodecyl phosphate is superior to the composition according to Comparative Example 1B containing dodecyl sulfate instead of isodecyl phosphate. It had antiviral properties (sterilizing properties) and antiviral properties, and was also excellent in durable antiviral properties (antiviral properties after wiping).
  • Non-aqueous processing using active energy curable (UV curable) resins 4.1 Preparation of compound N , the neutralized salt shown in Table 1 above was added to adjust the alkyl phosphate salt to 100% by mass. The types of alkyl groups and salts are shown in Table 1 above.
  • Antibacterial/Antiviral Agent Composition Phosphate mono/diester as an antibacterial/antiviral agent, polyurethane (meth)acrylate oligomer, pentaerythritol tri/tetraacrylate, and photopolymerization initiator. , and further mixed with methyl ethyl ketone to prepare an antibacterial/antiviral agent composition having an active ingredient amount (amount of ingredients other than catalyst and solvent) of 50% by mass.
  • the blending amounts shown in Table 5 are values converted into the solid content of each component. Also, the amount of the photopolymerization initiator to be blended was set to 5.3 parts by mass with respect to 100 parts by mass of the active ingredient.
  • the antiviral activity value was measured according to ISO21702:2019, and the antiviral performance of the leather-like laminate after the antibacterial/antiviral agent composition was fixed was evaluated.
  • influenza A virus H3N2 ATCC VR-1679 was used.
  • Antiviral activity value R (Ut-U0)-(At-U0).
  • U0 is the average common logarithm (PFU/cm 2 ) of the number of plaques recovered from the raw sample immediately after inoculation
  • Ut is the average common logarithm (PFU/cm 2 ) of the number of plaques recovered from the raw sample after 24 hours.
  • At is the mean common logarithm (PFU/cm 2 ) of the number of plaques recovered from the processed samples after 24 hours.
  • PFU/cm 2 the mean common logarithm
  • the antibacterial activity value was measured according to JIS Z2801:2010 to evaluate the antibacterial performance of the leather-like laminate after the antibacterial/antiviral agent composition was fixed.
  • Staphylococcus aureus NBRC12732 was used as the bacterium. The higher the activity value, the better the antibacterial properties. In this example, the antibacterial activity was judged to be good when the antibacterial activity value was 2.0 or more.
  • the composition according to Example 1C containing isodecyl phosphate is the composition according to Comparative Example 1C that does not contain an antibacterial/antiviral agent, and the composition according to Comparative Example 1C that does not contain an isodecyl phosphate. It was possible to impart superior antibacterial and antiviral properties to the leather-like laminate as compared with the composition according to Comparative Example 2C containing a sulfate ester.
  • urethane resin (1) having no hydroxyl group A lacquer-type urethane resin ("Barnock 16-411" manufactured by DIC Corporation, weight average molecular weight: 29796, glass transition point (Tg): 20 ° C.) was used. .
  • HDI-based isocyanurate-type curing agent Isocyanurate-type hexamethylene diisocyanate (“Duranate TPA-100” manufactured by Asahi Kasei Corporation, viscosity: 1350 mPa ⁇ s/25° C.) was used.
  • the antiviral activity value was measured according to ISO21702:2019, and the antiviral performance of the polyester film after coating treatment with the antibacterial/antiviral agent composition was evaluated.
  • influenza A virus H3N2 ATCC VR-1679 was used.
  • Antiviral activity R (Ut-U0)-(At-U0).
  • U0 is the average common logarithm (PFU/cm 2 ) of the number of plaques recovered from the raw sample immediately after inoculation
  • Ut is the average common logarithm (PFU/cm 2 ) of the number of plaques recovered from the raw sample after 24 hours.
  • At is the mean common logarithm (PFU/cm 2 ) of the number of plaques recovered from the processed samples after 24 hours.
  • compositions according to Examples 1D to 4D containing isodecyl phosphate are more polyester than the composition according to Comparative Example 1D containing dodecyl sulfate instead of isodecyl phosphate. It was possible to impart excellent antiviral properties to the film.
  • a phosphate monoester having an alkyl group having 8 to 20 carbon atoms or a salt thereof (general formula (A) above) and a phosphate diester having an alkyl group having 8 to 20 carbon atoms or a salt thereof (general formula (B) ) and/or antibacterial and antiviral composition.
  • anionic surfactants tend to be less irritating to the skin than cationic surfactants.
  • the antibacterial/antiviral agent composition of the present disclosure also has the advantage of low skin irritation.

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Abstract

L'invention concerne une composition d'agent antibactérien/antiviral présentant d'excellentes propriétés antivirales. La composition d'agent antibactérien/antiviral de la présente invention comprend au moins l'un parmi un monoester d'acide phosphorique ayant un groupe alkyle en C8-20, ou un sel de celui-ci, et un diester d'acide phosphorique ayant un groupe alkyle en C8-20, ou un sel de celui-ci.
PCT/JP2022/029827 2021-08-05 2022-08-03 Composition d'agent antibactérien/antiviral, structure antibactérienne/antivirale et procédé de production de structure antibactérienne/antivirale Ceased WO2023013687A1 (fr)

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