WO2023190471A1 - Dispersion contenant des microparticules métalliques présentant une propriété antimicrobienne avec une excellente stabilité à long terme - Google Patents

Dispersion contenant des microparticules métalliques présentant une propriété antimicrobienne avec une excellente stabilité à long terme Download PDF

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WO2023190471A1
WO2023190471A1 PCT/JP2023/012418 JP2023012418W WO2023190471A1 WO 2023190471 A1 WO2023190471 A1 WO 2023190471A1 JP 2023012418 W JP2023012418 W JP 2023012418W WO 2023190471 A1 WO2023190471 A1 WO 2023190471A1
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fine particles
dispersion
metal fine
acid
mass
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PCT/JP2023/012418
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English (en)
Japanese (ja)
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聡太朗 簾
和彰 大橋
泰啓 小坂
章子 小金井
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東洋製罐グループホールディングス株式会社
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Priority to JP2023547056A priority Critical patent/JP7392905B1/ja
Publication of WO2023190471A1 publication Critical patent/WO2023190471A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
    • B22F1/102—Metallic powder coated with organic material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof

Definitions

  • the present invention relates to a dispersion liquid containing fine metal particles coated with ascorbic acid or the like, a dispersant, and/or a binder resin and having antimicrobial properties with excellent stability over time.
  • Patent Document 1 listed below describes an antiviral composition containing monovalent copper compound fine particles, a reducing agent, and a dispersion medium, and having a pH of 6 or less.
  • Patent Document 2 describes a copper-supported oxide having an average secondary particle size of 80 nm to 600 nm, in which at least one of copper particles and copper compound particles is supported on oxide particles, and a copper-supported oxide having an average secondary particle size of 1 ⁇ m.
  • Antiviral coatings with ⁇ 15 ⁇ m barium sulfate and a water-repellent resin binder have been described.
  • metal fine particles tend to aggregate and are difficult to disperse uniformly, especially when the dispersion is used as an antiviral composition, or when coated with a binder resin for paint. When used as a coating film, it has been difficult to efficiently exhibit the antiviral properties of metal fine particles.
  • a dispersion liquid with improved dispersibility of metal fine particles the present inventors have proposed a dispersion liquid containing metal fine particles coated with a fatty acid (Patent Documents 3 and 4).
  • Patent No. 5194185 Japanese Patent Application Publication No. 2015-205998 Japanese Patent Application Publication No. 2017-128809 JP 2018-100255 Publication
  • the surface of the metal fine particles is coated with a fatty acid and/or an ester compound of the fatty acid, thereby preventing agglomeration of the metal fine particles and dispersing the metal fine particles.
  • This enables uniform dispersion in the medium.
  • fine metal particles are used in combination with a certain dispersant or binder resin for paint, it has been possible to exhibit the excellent antiviral properties of fine metal particles immediately after preparing the dispersion liquid.
  • this dispersion liquid is stored for a long period of time, a problem arises in that the effects of the metal fine particles, such as antiviral properties, cannot be obtained.
  • the present inventors conducted intensive research and found that the effect of metal fine particles disappears when the dispersant or binder resin has an acidic functional group such as a carboxyl group. It was found that this was caused by ionization of the metal fine particles due to their coexistence with acidic functional groups.
  • an object of the present invention is to effectively suppress the ionization of metal fine particles in a dispersion containing a dispersant having an acidic functional group and/or a binder resin having an acidic functional group, and to improve the antimicrobial properties of the metal fine particles.
  • This invention relates to a dispersion liquid that can stably express over a long period of time.
  • a stabilizer comprising at least one of ascorbic acid, a derivative of ascorbic acid, and a reducing polyhydric phenol, metal fine particles, and a dispersant having an acidic functional group and/or a binder having an acidic functional group
  • a dispersion liquid containing a resin and the stabilizer in an amount of 150 parts by mass or more based on 100 parts by mass of metal fine particles.
  • the metal ion concentration derived from the metal fine particles is 100 ppm or less; (2) the content of the metal fine particles is 0.001 to 10% by mass; (3) the content of the stabilizer is 0.0015 to 15% by mass; (4) the surface of the metal fine particles is coated with the stabilizer; (5) the metal fine particles are made of copper or a copper compound, or silver or a silver compound; (6) the acidic functional group of the dispersant and binder resin is a carboxyl group; (7) the binder resin is any one of acrylic resin, polyester resin, and cellulose resin; (8) the surface of the metal fine particles is further coated with fatty acid and/or fatty acid ester; is suitable.
  • the present invention also provides metal fine particles whose surfaces are coated with a stabilizer comprising at least one of ascorbic acid, an ascorbic acid derivative, and a reducing polyhydric phenol. .
  • the metal fine particles of the present invention are preferably metal fine particles made of copper or a copper compound, or silver or a silver compound.
  • an antimicrobial molded article having a coating made of the above dispersion.
  • the surface of the metal fine particles is coated with a stabilizer consisting of at least one of ascorbic acid, a derivative of ascorbic acid, and a reducing polyhydric phenol, so that acidic functional groups such as carboxyl groups
  • a stabilizer consisting of at least one of ascorbic acid, a derivative of ascorbic acid, and a reducing polyhydric phenol, so that acidic functional groups such as carboxyl groups
  • the metal fine particles can be uniformly dispersed in the dispersion without agglomerating. Even when a coating film is formed as a product, it is possible to impart excellent antimicrobial properties to the coating film.
  • antimicrobial property is a general term for antiviral property, antifungal property, antibacterial property, etc., and refers to the effect of inactivating viruses and the like.
  • a coating dispersion in which a dispersion containing a dispersant having an acidic functional group obtained in Example 1 and Comparative Examples 1, 4, and 5 was mixed with an acrylic resin emulsion having an acidic functional group as a binder resin A
  • XRD X-ray diffraction
  • Example 6 and Comparative Example 7 in which the dispersions obtained in Example 1 and Comparative Example 1 were mixed with an acrylic resin emulsion having an acidic functional group as binder resin A, immediately after preparation and It is a photograph showing changes in appearance after a day has passed.
  • the active ingredient exhibiting antimicrobial properties is metal fine particles, and the oxidizing power of active oxygen generated from these metal fine particles denatures and decomposes the proteins of microorganisms such as viruses, and the metal fine particles also denature and decompose proteins of microorganisms such as viruses. It is thought that these metal particles can denature proteins and inactivate viruses by reacting with the thiol groups of Then, over time, the metal fine particles and this acidic functional group react with each other, resulting in metal ionization, making it impossible to obtain the desired antimicrobial properties.
  • the dispersion contains a dispersant having an acidic functional group and/or a binder resin having an acidic functional group, at least one of ascorbic acid, a derivative of ascorbic acid, and a reducing polyhydric phenol is used.
  • the stabilizing agent having a reducing property is contained in an amount of 150 parts by mass or more per 100 parts by mass of metal fine particles, thereby making it possible to exhibit the effect of suppressing ionization of metal fine particles. becomes.
  • a suitable content of the stabilizer for the metal fine particles is 150 to 8000 parts by mass of the stabilizer per 100 parts by mass of the metal fine particles when the dispersion liquid contains only a dispersant having an acidic group.
  • the stabilizer can be contained in an amount of 150 to 20,000 parts by weight, preferably 200 to 17,000 parts by weight, and more preferably 200 to 15,000 parts by weight per 100 parts by weight.
  • the content of the stabilizer there is no upper limit on the content of the stabilizer as long as the excess stabilizer not used to coat the surface of the metal fine particles can be uniformly dispersed in the dispersion; It is preferable that the content of the stabilizer is 15% by mass or less, further 8% by mass or less, particularly 6% by mass or less, and this makes it possible to use water or an aqueous solvent as a dispersion medium. Even when the stabilizer is present, it is possible to uniformly disperse the stabilizer, and this is also preferable from the economic point of view. Furthermore, if the content of the stabilizer becomes excessive, the appearance of the coating film obtained by applying the dispersion or coating dispersion will be impaired, so the above range is preferable.
  • the surface of the metal fine particles is coated and protected with a reducing stabilizer, thereby suppressing the reaction between the metal fine particles and the acidic functional groups of the dispersant and/or resin binder. It becomes possible to suppress the ionization of metal particles and maintain the state of metal fine particles stably for a long period of time.
  • metal particles which are active ingredients that exhibit antimicrobial properties, include metals such as copper, silver, gold, zinc, and nickel, and compounds of these metals. Copper or silver, or a compound of these metals, which can be expressed, is preferable, and copper or a copper compound, especially copper or a monovalent copper compound, is preferable from the viewpoint of excellent antiviral properties.
  • the metal fine particles preferably have an average primary particle size in the range of 10 to 500 nm, particularly 10 to 200 nm. When the average primary particle of the metal fine particles is within the above range, it becomes possible to efficiently exhibit excellent antimicrobial performance.
  • metal fine particles with such a small average primary particle size can efficiently generate active oxygen due to their high contact rate with oxygen, and can exhibit excellent antimicrobial performance.
  • the metal fine particle powder is preferably composed of primary particles having the above-mentioned average primary particle size, and the average secondary particle size is preferably in the range of 100 nm to 500 ⁇ m, particularly 100 nm to 100 ⁇ m, so that it can be obtained in a powder state.
  • the metal fine particles can be easily dispersed in a dispersion medium, and when mixed with a binder resin to form a paint dispersion, it has excellent handling properties such as coatability.
  • the average primary particle size in this specification refers to the average of two metal particles with no gaps between them, and the average secondary particle size is the average of the metal particles with no gaps between them. Particles are particles that are packed together and are averaged. Furthermore, the primary particle size can be measured using a scanning electron microscope (SEM), and the secondary particle size can be measured using dynamic light scattering (DLS).
  • SEM scanning electron microscope
  • DLS dynamic light scattering
  • the surface of the metal fine particles used in the present invention be coated with a fatty acid and/or a fatty acid ester. This, together with being coated with the above-mentioned stabilizer, further suppresses aggregation and oxidation of the metal fine particles, making it possible to obtain excellent antimicrobial properties and dispersibility.
  • the fatty acids that coat the surface of the metal fine particles include caprylic acid, capric acid, lauric acid, myristic acid, stearic acid, oleic acid, palmitic acid, n-decanoic acid, paratoic acid, succinic acid, malonic acid, tartaric acid, malic acid, Examples include glutaric acid, adipic acid, acetic acid, etc., and combinations of a plurality of these may be used, but palmitic acid and stearic acid are particularly preferred.
  • the ester compound that coats the surface of the metal fine particles is preferably an ester compound derived from fatty acids and polyols, which are raw materials in the method for producing metal fine particle powder of the present invention, which will be described later.
  • the metal fine particles are preferably contained in the dispersion in an amount of 0.001 to 10% by weight, preferably 0.002 to 5% by weight, particularly 0.05 to 1% by weight. Furthermore, as mentioned above, in the dispersion of the present invention, the ionization of the metal fine particles due to the reaction between the metal fine particles and the acidic functional group of the dispersant and/or the binder resin is suppressed. The metal ion concentration is reduced to 100 ppm or less, particularly 60 ppm or less.
  • the stabilizer used in the present invention is a stabilizer composed of at least one of ascorbic acid, a derivative of ascorbic acid, and a reducing polyhydric phenol, and has a reducing property capable of suppressing the ionization of metal fine particles, and has a reducing property that can suppress the ionization of metal fine particles.
  • a low molecular weight material that can be easily coated on a surface is preferred.
  • the solvent of the dispersion is water or an aqueous solvent, it is preferable that the solvent exhibits water solubility.
  • Ascorbic acid or its derivatives include ascorbic acid, calcium ascorbate, sodium ascorbate, ascorbic acid-2-glucoside, 2-o-methylascorbic acid, 3-o-methylascorbic acid, 2-o-ethylascorbic acid, 3-o-ethyl ascorbic acid, ascorbic acid-6-palmitate, ascorbic acid-6-stearate, ascorbic acid dipalmitate, 6-o-palmitoyl ascorbic acid-2-o-phosphate, 6-o-acyl -2-o- ⁇ -D-glucopyranosyl-L-ascorbic acid, magnesium ascorbic acid-2-phosphate, ascorbic acid-2-phosphate, sodium ascorbic acid-2-phosphate, ascorbic acid-2-sulfate, ascorbic acid Examples include potassium acid-2-sulfate, barium ascorbic acid-2-sulfate, disodium ascorbic acid-2-sulfate, and trisodium ascorbic acid-2-phosphate.
  • polyhydric phenols having reducing properties examples include polyhydric phenols such as resorcinol, alkylresorcinol, pyrogallol, catechol, alkylcatechol, hydroquinone, alkylhydroquinone, and phloroglucinol.
  • L-ascorbic acid can be preferably used from the viewpoints of coating properties on metal fine particles, reducing properties, and water solubility.
  • Dispersant with acidic functional group it is desirable to contain a dispersant in order to improve the dispersibility of metal fine particles in the dispersion. Since the metal fine particles of the present invention are coated with the above-mentioned stabilizer, ionization of the metal fine particles is suppressed, and therefore is particularly suitable when using a dispersant having an acidic functional group.
  • the dispersant preferably has at least an acidic functional group such as a carboxyl group, an acid anhydride group, a sulfonic acid group, a phosphoric acid group, and in addition to the above acidic functional groups, it also has an amino group, an imino group, an ammonium base,
  • the wetting and dispersing agent may have a star polymer structure having a basic functional group such as a heterocyclic group having a basic nitrogen atom or a comb-shaped polymer structure.
  • the dispersant preferably has an acid value in the range of 3 to 100 mgKOH/g, preferably 4 to 30 mgKOH/g, particularly 5 to 20 mgKOH/g.
  • the storage stability of the dispersion may be lower than when it is within the above range, whereas if the acid value is higher than the above range, the storage stability of the dispersion may be lower than when it is within the above range. There is a risk that the water resistance of the coating film will be lower than that of the above.
  • the dispersant used in the present invention preferably has a weight average molecular weight of 1,000 or more.
  • the weight average molecular weight of the dispersant is less than 1,000, sufficient steric hindrance by the acidic functional group or the acidic functional group and the basic functional group cannot be obtained.
  • the side chain or main chain skeleton to which these functional groups are bonded is not particularly limited, and can be made of polyester, polyacrylic, polyether, polyoxyalkylene, or the like.
  • the acidic functional group or the acidic functional group and the basic functional group of the dispersant strongly adsorb to the metal fine particles, giving the metal fine particles polarity, causing the metal fine particles to repel each other due to electric charge, and causing the metal fine particles to It is thought that the presence of a modifying group of a certain length on the surface forms steric hindrance, and as a result, the metal fine particles can be uniformly dispersed in the solvent without aggregation or sedimentation.
  • Dispersants that can be suitably used in the metal fine particle-containing dispersion of the present invention include, but are not limited to, DISPERBYK-102, 180, 182, 184, 190, 191, 192, 193, 194N, 199, 2060, 2061, 2090, 2095, 2096, 2155, 154 (manufactured by Big Chemie), Sokalan CP9, Lupasol FG, Pluronic PE6400, Pluronic PE6800, Lutropur MSA, Sokalan PA110S, Sokala n CP12S, Sokalan CP13S, Sokalan VA 64P, Lupasol HF, Plurafac LF300 , Pluronic RPE1740, Pluronic RPE3110, Degressal SD40 (manufactured by BASF), SC-0505K, AFB-1521, SC-1015F, AKM-0531, AKM-1511-60 (manufactured by NOF Corporation), among which In particular, DISPERB
  • the dispersant is preferably contained in an amount of 50 to 1000 parts by mass, particularly 100 to 500 parts by mass, per 100 parts by mass of the metal fine particles. If the amount of dispersant is less than the above range, the dispersibility of the metal fine particles will be inferior to that in the above range, while on the other hand, even if the amount of dispersant is greater than the above range, there will be no further effect. There is no hope of improving the performance, and there is a possibility that the economic efficiency will be inferior.
  • the dispersion of the present invention can form a coating film (hereinafter, when it contains a binder resin, it may be referred to as a "paint dispersion").
  • a coating film hereinafter, when it contains a binder resin, it may be referred to as a "paint dispersion”
  • the metal fine particles of the present invention are coated with the above-mentioned stabilizer, the ionization of the metal fine particles is suppressed even when the binder resin has an acidic functional group. This is particularly suitable when using a binder resin having an acidic functional group such as an acid group or a phosphoric acid group.
  • binder resins examples include phenol resins, epoxy resins, urethane resins, melamine resins, urea resins, alkyd resins, unsaturated polyester resins, silicone resins, acrylic resins, and polyester resins, which have been conventionally used as paints.
  • the dispersion of the present invention is preferably an aqueous dispersion, water-dispersible or water-soluble acrylic resins, polyester resins, and cellulose resins can be suitably used.
  • an electron beam curable resin can be used, but a self-crosslinking acrylic resin that does not use a curing agent can be particularly preferably used.
  • the binder resin is preferably added in an amount of 5,000 to 100,000 parts by mass per 100 parts by mass of the metal fine particles.
  • water-dispersible or water-soluble acrylic resins include acrylic resin emulsions obtained by emulsion polymerization of ethylenically unsaturated monomers having acidic functional groups such as carboxyl groups, acid anhydride groups, sulfonic acid groups, and phosphoric acid groups. can.
  • carboxyl group-containing ethylenically unsaturated monomers such as acrylic acid, methacrylic acid, crotonic acid, isocrotonic acid, propyl acrylic acid, isopropyl acrylic acid, itaconic acid, maleic anhydride, and fumaric acid
  • p-vinylbenzene examples include sulfonic acid-containing ethylenically unsaturated monomers such as sulfonic acid and p-acrylamidopropanesulfonic acid, and phosphoric acid group-containing ethylenically unsaturated monomers such as phosphoric acid monoester of 2-hydroxyethyl acrylate.
  • an acrylic resin emulsion comprising a carboxyl group-containing ethylenically unsaturated monomer is preferred.
  • the acrylic resin emulsion can also contain (meth)acrylic acid alkyl esters and hydroxyl group-containing ethylenically unsaturated monomers.
  • the acid value of the acrylic resin is preferably in the range of 3 to 100 mgKOH/g. If it is lower than the above range, there is a risk that the storage stability of the dispersion will decrease, and when forming a coating, there is a risk that sufficient curability may not be obtained.On the other hand, if it is lower than the above range This may result in a decrease in polymerization stability and a decrease in the water resistance of the coating film.
  • the number average molecular weight of the acrylic resin is not particularly limited, but is preferably in the range of 10,000 to 50,000.
  • Water-dispersible or water-soluble polyester resins include polyester resins containing acidic functional groups such as carboxyl groups, acid anhydride groups, sulfonic acid groups, and phosphoric acid groups, and these components are included in the polyester resin dispersion. Although it may be coordinated on the surface, it is preferable that the monomer having the acidic functional group is present in the polyester resin skeleton as a copolymerization component.
  • Such monomers include carboxylic anhydrides such as phthalic anhydride, succinic anhydride, maleic anhydride, trimellitic anhydride, itaconic anhydride, citraconic anhydride, 5-sulfoisophthalic acid, 4-sulfonaphthalene-2
  • Examples include metal salts of sulfonic acid-containing monomers such as , 7-dicarboxylic acid, and 5(4-sulfophenoxy)isophthalic acid.
  • an acrylic resin-modified polyester resin obtained by graft-polymerizing a vinyl monomer having an acidic functional group onto a polyester resin may be used.
  • the monomer to be combined with the monomer having an acidic functional group to form a polyester resin is not particularly limited as long as it is commonly used in the polymerization of polyester resins.
  • the polycarboxylic acid component constituting the polyester resin include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, orthophthalic acid, and naphthalene dicarboxylic acid, succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, and dodecanedione.
  • acids aliphatic dicarboxylic acids such as dimer acid, unsaturated dicarboxylic acids such as (anhydrous) maleic acid, fumaric acid, terpene-maleic acid adducts, 1,4-cyclohexanedicarboxylic acid, tetrahydrophthalic acid, hexahydroisophthalic acid,
  • examples include alicyclic dicarboxylic acids such as 1,2-cyclohexenedicarboxylic acid, trivalent or higher polyhydric carboxylic acids such as (anhydrous) trimellitic acid, (anhydrous) pyromellitic acid, and methylcyclohexenetricarboxylic acid. , one type or two or more types can be selected and used from these.
  • polyhydric alcohol component constituting the polyester resin examples include ethylene glycol, propylene glycol (1,2-propanediol), 1,3-propanediol, 1,4-butanediol, 1,2-butanediol, 1 , 3-butanediol, 2-methyl-1,3-propanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 2-ethyl- 2-Butyl-1,3-propanediol, 2,4-diethyl-1,5-pentanediol, 1-methyl-1,8-octanediol, 3-methyl-1,6-hexanediol, 4-methyl- Aliphatic glycols such as 1,7-heptanediol, 4-methyl-1,8-octanediol, 4-propy
  • the acid value of the polyester resin is preferably in the range of 3 to 100 mgKOH/g. If it is lower than the above range, there is a risk that the storage stability of the dispersion will be lower than when it is within the above range, and when forming a coating, there is a risk that sufficient curability may not be obtained. be. On the other hand, if the amount exceeds the above range, the polymerization stability may be lowered compared to the case where the amount is within the above range, and the water resistance of the coating film may also be lowered.
  • the number average molecular weight of the polyester resin is not particularly limited, but is preferably in the range of 5,000 to 30,000.
  • cellulose resins include cellulose and/or cellulose derivatives, and examples of cellulose derivatives include cellulose ether in which some or all of the hydroxyl groups of cellulose are etherified, and cellulose in which some or all of the hydroxyl groups of cellulose are esterified. Examples include esters.
  • cellulose resins examples include cellulose ethers such as methylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxyethylmethylcellulose, hydroxypropylmethylcellulose, hydroxybutylmethylcellulose, ethylhydroxyethylcellulose, carboxymethylcellulose, carboxyethylcellulose, and carboxymethylhydroxyethylcellulose;
  • cellulose ethers such as methylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxyethylmethylcellulose, hydroxypropylmethylcellulose, hydroxybutylmethylcellulose, ethylhydroxyethylcellulose, carboxymethylcellulose, carboxyethylcellulose, and carboxymethylhydroxyethylcellulose
  • cellose esters such as cellulose acetate, cellulose propionate, cellulose butyrate, cellulose acetate propionate, and cellulose acetate butyrate, and one or more types thereof can be selected and used.
  • carboxyalkylcelluloses such as carboxymethylcellulose and
  • Dispersion medium In the dispersion of the present invention, the following solvents can be used as the dispersion medium for dispersing the metal fine particles. , various water solvents such as ion-exchanged water and pure water, ester solvents such as methyl acetate, ethyl acetate, and butyl acetate, hydrocarbon solvents such as hexane, heptane, toluene, xylene, and cyclohexane, methyl isobutyl ketone, methyl ethyl ketone, and cyclohexanone.
  • various water solvents such as ion-exchanged water and pure water, ester solvents such as methyl acetate, ethyl acetate, and butyl acetate, hydrocarbon solvents such as hexane, heptane, toluene, xylene, and cyclohexane, methyl isobutyl ketone, methyl
  • aqueous solvents or aqueous mixed solvents can be preferably used, and particularly water or a mixed solvent of water and an amphipathic organic solvent such as alcohol is preferably used. I can do it.
  • metal fine particles can be uniformly dispersed in the various dispersion media described above for a long period of time without agglomeration or sedimentation. It is preferable that the liquid contains metal fine particles in an amount of 10% by mass or less, particularly 0.001 to 1% by mass.
  • a dispersant having an acidic functional group and/or a binder resin having an acidic functional group, a stabilizer and a solvent, an antioxidant, a surfactant, a curing agent, a catalyst, etc. , a polymerization initiator, and other components as necessary is added to a known formulation. It can also be contained.
  • the dispersion of the present invention can be prepared by the following manufacturing method.
  • First step A fatty acid metal salt is added to a polyol and heated to prepare a polyol solution containing metal fine particles whose surfaces are coated with a fatty acid and/or an ester compound of the fatty acid and the polyol.
  • the heating temperature is preferably lower than the decomposition starting temperature of the fatty acid metal salt used, and the heating and mixing time is preferably 60 to 360 minutes. If the heating temperature is equal to or higher than the decomposition start temperature of the fatty acid metal salt, the fatty acid and/or ester compound will not be coated on the metal fine particles, and the metal fine particles may be oxidized.
  • the decomposition start temperature is defined by JIS K 7120.
  • the amount of fatty acid metal salt blended is preferably in the range of 0.1 to 5% by mass based on the polyol.
  • the amount of the fatty acid metal salt is less than the above range, there is a possibility that sufficient antimicrobial properties cannot be imparted to the dispersion compared to when the amount is within the above range.
  • the amount of the fatty acid metal salt is greater than the above range, the economical efficiency is inferior to when the amount is within the above range.
  • the polyol include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, polypropylene glycol, and glycerin, which are appropriately selected in combination with the low-boiling solvent described below.
  • a polyol solution containing fine metal particles coated with a fatty acid and/or an ester compound of the fatty acid and a polyol is mixed with a low boiling point solvent to prepare a mixed solution.
  • the low boiling point solvent is preferably added in an amount of 10 to 200% by mass based on the polyol.
  • Low boiling point solvents include esters such as methyl acetate, ethyl acetate, and butyl acetate, hydrocarbons such as hexane, heptane, toluene, xylene, and cyclohexane, and ketones such as methyl isobutyl ketone, methyl ethyl ketone, and cyclohexanone.
  • ester solvents are preferred, and among them, butyl acetate, ethyl acetate, and methyl isobutyl ketone are preferably used.
  • the low boiling point solvent is not compatible with the polyol, and it is preferable to combine the polyol and the low boiling point solvent so that the difference in solubility parameter (Sp value) between the polyol and the low boiling point solvent is 3 or more.
  • Sp value solubility parameter
  • Sp value diethylene glycol
  • butyl acetate Sp value: 8.4
  • the metal particles are sufficiently coated with the ester compound of fatty acid and polyol, so there is no need to intentionally blend the ester compound into the low boiling point solvent, but depending on the amount of coating in the first step, can also be blended.
  • a solution containing fine metal particles coated with a fatty acid and/or an ester compound of the fatty acid and the polyol in a polyol is obtained. Removal of the low boiling point solvent can be performed by conventionally known separation methods such as decantation and extraction.
  • recovery of the metal fine particles from the polyol can be performed by a conventionally known separation method such as membrane separation, centrifugation, decantation, etc., but is not limited thereto, but membrane separation is preferable.
  • the separated metal fine particles are thoroughly washed with water or a low boiling point solvent such as butyl acetate or hexane, and then heated and dried at 40 to 50°C for 60 to 360 minutes to sufficiently remove moisture, thereby removing fatty acids and esters. It is possible to obtain dry metal fine particle powder having a compound coating amount of 0.1 to 20% by mass.
  • the metal fine particle powder is added and mixed.
  • the dispersant is preferably added in an amount of 50 to 1000 parts by mass per 100 parts by mass of the metal fine particles.
  • a stabilizer such as L-ascorbic acid is added in an amount of 150 parts by mass or more per 100 parts by mass of the metal fine particles, and further mixing and dispersion treatment is performed to form the metal fine particles, the stabilizer, and the dispersion.
  • a dispersion containing the agent can be obtained.
  • the coating dispersion when the coating dispersion further contains a binder resin containing an acidic functional group, the dispersion prepared in the fourth step described above, the binder resin and It is prepared by uniformly mixing with a curing agent if necessary.
  • the binder resin is preferably added in an amount of 5,000 to 100,000 parts by mass per 100 parts by mass of the metal fine particles.
  • Metal fine particles containing a stabilizer in a low boiling point solvent can be produced by the following method in addition to the above-mentioned production method. That is, in the first step of the first production method described above, fatty acids and/or By preparing a dispersion of metal fine particles coated with the fatty acid ester compound and then passing through the second to fourth steps described above, a metal fine particle dispersion further containing a stabilizer can be obtained.
  • a fine metal particle powder containing the agent can be produced. That is, the polyol solution containing the metal fine particles coated with the fatty acid and/or the ester compound of the fatty acid and the polyol obtained in the first step of the first manufacturing method described above is used as it is, and the metal fine particles recovered from this solution are used. may be used.
  • the viscosity of the polyol dispersion is high due to excess fatty acid metal salts, free fatty acids or ester compounds, and other impurities, and it is difficult to remove the low boiling point solvent as it is, so dilute it with ethanol etc. to reduce the viscosity.
  • After lowering the temperature remove the solvent.
  • the fatty acid metal salt by heating in an inert atmosphere, adding the above-mentioned stabilizer or a stabilizer and an ester compound, and pulverizing and mixing it, it is possible to coat the fatty acid metal salt with at least the stabilizer.
  • the dispersion of the present invention can also be used as it is by spraying it onto a base material such as a nonwoven fabric, a resin film, or a textile product, and can be used as a molded article with a coating made of the dispersion of the present invention formed on the surface of the base material. I can do it.
  • a molded article can be obtained by preparing a paint dispersion containing a binder resin, applying this to the above-mentioned base material, and then baking and drying it to form a coating (coating film).
  • molded objects such as films, sheets, nonwoven fabrics, fibers, etc. can also be formed directly from the above coating dispersion and used.
  • Example 1 ⁇ Preparation of dispersion liquid containing metallic copper fine particles and dispersant> (Example 1) DIPERBYK-190 (manufactured by BYK Chemie, acid value 10 mgKOH/g) as a dispersant was added to distilled water in an amount of 100 parts by mass based on 100 parts by mass of metallic copper fine particles, and the mixture was stirred. Next, the metallic copper fine particle powder produced above was added so that the metallic copper component was 0.1% by mass, and ultrasonication was performed for 10 minutes.
  • DIPERBYK-190 manufactured by BYK Chemie, acid value 10 mgKOH/g
  • L-ascorbic acid was added in an amount of 1000 parts by mass based on 100 parts by mass of metallic copper microparticles, and ultrasonication was further performed for 10 minutes to obtain an ascorbic acid-containing metallic copper microparticle dispersion.
  • Example 2 A dispersion liquid was prepared in the same manner as in Example 1, except that the proportion of L-ascorbic acid was changed to 200 parts by mass per 100 parts by mass of metallic copper fine particles.
  • Example 3 A dispersion liquid was prepared in the same manner as in Example 1 except that the proportion of L-ascorbic acid was changed to 500 parts by mass per 100 parts by mass of metallic copper fine particles.
  • Example 4 A dispersion liquid was prepared in the same manner as in Example 1 except that L-ascorbic acid was changed to 3-o-ethyl-L-ascorbic acid and 6000 parts by mass was added to 100 parts by mass of metal copper fine particles.
  • Example 5 A dispersion liquid was prepared in the same manner as in Example 1 except that L-ascorbic acid was changed to pyrogallol, which is a polyhydric phenol having reducing properties.
  • Example 1 A dispersion was prepared in the same manner as in Example 1 except that L-ascorbic acid was not added.
  • Example 2 A dispersion was prepared in the same manner as in Example 1, except that L-ascorbic acid and DISPERBYK-190 were not added.
  • Example 3 A dispersion liquid was prepared in the same manner as in Example 1, except that the proportion of L-ascorbic acid was changed to 100 parts by mass relative to 100 parts by mass of metallic copper fine particles.
  • Example 4 A dispersion liquid was prepared in the same manner as in Example 1 except that citric acid was used instead of L-ascorbic acid.
  • Example 5 A dispersion liquid was prepared in the same manner as in Example 1 except that L-ascorbic acid was changed to sodium phosphinate monohydrate.
  • Example 6 A dispersion liquid was prepared in the same manner as in Example 1 except that L-ascorbic acid was changed to D-maltose monohydrate.
  • ⁇ Zeta potential measurement method For the zeta potential, a zeta potential/particle size/molecular weight measurement system ELSZ-2000ZS manufactured by Otsuka Electronics Co., Ltd. was used. The measurement was carried out using a standard cell unit at a measurement voltage of 60V. A change in the absolute value of the zeta potential compared to Comparative Example 1 in which no L-ascorbic acid was added indicates that L-ascorbic acid is acting on the surface of the metallic copper fine particles. Measurements were made for Examples 1 to 5 and Comparative Examples 1 to 6. The results are shown in Table 1.
  • Example 11 4.0% by mass of the metallic copper fine particle dispersion of Example 1 so that the metal component concentration was 0.1% by mass based on the solid content of binder resin B (self-crosslinking acrylic acid ester emulsion polymer), A paint dispersion was prepared by mixing 8.9% by mass of binder resin B, 86.6% by mass of pure water, and 0.5% by mass of ascorbic acid.
  • binder resin B self-crosslinking acrylic acid ester emulsion polymer
  • FIG. 1 shows X-ray diffraction (XRD) charts of the paint dispersions obtained in Example 6 and Comparative Examples 7, 10, and 11 after 3 months of preparation. It can be seen that metallic copper fine particles are present in the paint dispersion prepared in Example 6 even after 3 months have elapsed.
  • FIG. 2 shows X-ray diffraction charts of the paint dispersions obtained in Example 6 and Comparative Example 7 immediately after preparation and after 3 days. In the paint dispersion of Comparative Example 7, which was the same as Example 6 except that L-ascorbic acid was not added, no diffraction peak of metallic copper fine particles was detected after 3 days.
  • Example 11 The coating dispersion prepared in Example 11 was applied to an untreated nonwoven fabric with a brush, and then dried in a dryer at 80° C. for 5 minutes. Thereafter, it was dried for 3 minutes in a dryer at 150°C to obtain a nonwoven fabric (molded body) on which metallic copper fine particles were immobilized.
  • a paint dispersion liquid (Comparative example 13) was prepared by mixing 8.9% by mass of binder resin B and 87.1% by mass of pure water. The prepared paint dispersion was applied to an unprocessed nonwoven fabric with a brush, and then dried in a dryer at 80° C. for 5 minutes. Thereafter, it was dried for 3 minutes in a dryer at 150°C to obtain a nonwoven fabric (molded body) on which metallic copper fine particles were immobilized.
  • the test was conducted in accordance with JIS L 1922.
  • (1) Host cells are infected with a virus, and after culturing, cell debris is removed by centrifugation to obtain a virus suspension.
  • (2) The virus suspension obtained in (1) above is diluted 10 times with sterile distilled water and used as a test virus suspension.
  • Table 3 shows the appearance evaluation of the paint dispersions containing binder resin B (Example 11 and Comparative Example 13) immediately after preparation and after storage for 7 days. Immediately after preparation, no change in color was observed in either Example 11 or Comparative Example 13, but when stored at room temperature for 7 days, the paint dispersion of Example 11 did not cause any change in color. However, on the other hand, a change in color was observed in the paint dispersion of Comparative Example 13.
  • the dispersion of the present invention can be directly applied to or impregnated into textile products, etc. to produce paper products, masks, wet tissues, air conditioner filters, air purifier filters, clothing, work clothes, curtains, carpets, automobile parts, packaging, etc. It becomes possible to apply antimicrobial coatings to textile products such as parts, freshness-preserving materials, sheets, towels, bath mats, diaper covers, stuffed animals, slippers, shoe insoles, and cleaning products such as wipers.
  • an aqueous solvent as a dispersion medium of a dispersion liquid, it can be used as a diluent for an aqueous composition, or by containing a binder resin in a dispersion liquid, an antimicrobial coating film can be formed on the surface. Molded products can be obtained. Furthermore, it can be used for medical devices, packaging films for medical devices, waste containers, garbage bags, wall and floor materials for nursing care facilities, hospitals, schools, and other public facilities, wax coating materials, vomit disposal tools, etc. can.

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Abstract

La présente invention concerne une dispersion contenant des microparticules métalliques, un dispersant ayant un groupe fonctionnel acide, et/ou une résine liante ayant un groupe fonctionnel acide. La présente invention peut fournir une dispersion qui est apte à présenter de manière stable, sur une longue période de temps, d'excellentes propriétés antimicrobiennes possédées par les microparticules métalliques, ladite dispersion contenant, dans une quantité égale ou supérieure à 150 parties en masse par rapport à 100 parties en masse des microparticules métalliques, un stabilisant composé d'au moins l'un parmi un acide ascorbique, un dérivé d'acide ascorbique et un phénol polyhydrique réducteur, ce qui supprime efficacement une ionisation des microparticules métalliques.
PCT/JP2023/012418 2022-03-31 2023-03-28 Dispersion contenant des microparticules métalliques présentant une propriété antimicrobienne avec une excellente stabilité à long terme WO2023190471A1 (fr)

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JP2009221505A (ja) * 2008-03-14 2009-10-01 Dowa Electronics Materials Co Ltd 没食子酸またはその誘導体に被覆された銀ナノ粒子
JP2014008506A (ja) * 2012-06-27 2014-01-20 Mitsubishi Materials Corp ＳｎＡｇＣｕ系はんだ粉末及びこの粉末を用いたはんだ用ペースト
JP2017137472A (ja) * 2016-01-29 2017-08-10 東洋インキＳｃホールディングス株式会社 導電性組成物、その製造方法、および導電性材料
JP2020063487A (ja) * 2018-10-18 2020-04-23 株式会社ノリタケカンパニーリミテド ＡｇＰｄコアシェル粒子およびその利用
JP2020147840A (ja) * 2019-03-16 2020-09-17 学校法人智香寺学園埼玉工業大学 ナノコロイド充填防錆金属材料、ナノコロイド混合防錆塗料及びナノコロイド粒子を用いた防錆方法
JP2020169387A (ja) * 2019-04-03 2020-10-15 東洋製罐グループホールディングス株式会社 金属銅微粒子粉末及びその製造方法
JP2022026615A (ja) * 2020-07-31 2022-02-10 京セラ株式会社 被覆銅粒子、被覆銅粒子の製造方法、銅ペースト、銅ペーストの製造方法、及び半導体装置

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009221505A (ja) * 2008-03-14 2009-10-01 Dowa Electronics Materials Co Ltd 没食子酸またはその誘導体に被覆された銀ナノ粒子
JP2014008506A (ja) * 2012-06-27 2014-01-20 Mitsubishi Materials Corp ＳｎＡｇＣｕ系はんだ粉末及びこの粉末を用いたはんだ用ペースト
JP2017137472A (ja) * 2016-01-29 2017-08-10 東洋インキＳｃホールディングス株式会社 導電性組成物、その製造方法、および導電性材料
JP2020063487A (ja) * 2018-10-18 2020-04-23 株式会社ノリタケカンパニーリミテド ＡｇＰｄコアシェル粒子およびその利用
JP2020147840A (ja) * 2019-03-16 2020-09-17 学校法人智香寺学園埼玉工業大学 ナノコロイド充填防錆金属材料、ナノコロイド混合防錆塗料及びナノコロイド粒子を用いた防錆方法
JP2020169387A (ja) * 2019-04-03 2020-10-15 東洋製罐グループホールディングス株式会社 金属銅微粒子粉末及びその製造方法
JP2022026615A (ja) * 2020-07-31 2022-02-10 京セラ株式会社 被覆銅粒子、被覆銅粒子の製造方法、銅ペースト、銅ペーストの製造方法、及び半導体装置

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