WO2022190859A1 - Metal nanoparticle-containing dispersion composition - Google Patents

Metal nanoparticle-containing dispersion composition Download PDF

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Publication number
WO2022190859A1
WO2022190859A1 PCT/JP2022/007233 JP2022007233W WO2022190859A1 WO 2022190859 A1 WO2022190859 A1 WO 2022190859A1 JP 2022007233 W JP2022007233 W JP 2022007233W WO 2022190859 A1 WO2022190859 A1 WO 2022190859A1
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Prior art keywords
fluorine
group
metal
dispersion composition
metal nanoparticle
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PCT/JP2022/007233
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French (fr)
Japanese (ja)
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尚史 ▲高▼林
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株式会社ダイセル
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Publication of WO2022190859A1 publication Critical patent/WO2022190859A1/en

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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
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/16—Metallic particles coated with a non-metal
    • 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
    • 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
    • B22F9/16—Making metallic powder or suspensions thereof using chemical processes
    • B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
    • B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions

Definitions

  • the present disclosure relates to a metal nanoparticle-containing dispersion liquid composition.
  • This application claims priority from Japanese Patent Application No. 2021-037127 filed in Japan on March 9, 2021, the content of which is incorporated herein.
  • transparent materials such as glass tend to lose their appearance and visibility due to the adhesion of dirt such as sebum due to contact with the skin and the adhesion of water droplets due to rainfall.
  • the surface is treated with a fluorine-containing coating agent or the like.
  • touch panel displays visibility and operability are important, so in addition to being required to have particularly high antifouling properties and dirt removal, they are operated by direct touch, so cleanliness and hygiene are required. It is also desired to have antibacterial properties.
  • coating agents are liquid compositions such as solutions and dispersions.
  • Various studies have been made to disperse metal nanoparticles well in a liquid composition.
  • a silver nanoparticle-containing dispersion is disclosed in which silver nanoparticles obtained by decomposition are dispersed in an alcoholic solvent.
  • Patent Document 1 since the metal nanoparticles in the dispersion of Patent Document 1 are inferior in dispersibility to the fluorine-based solvent blended in the fluorine-containing coating agent, it is difficult to obtain a uniform dispersion using the fluorine-based solvent. There was a problem that
  • an object of the present disclosure is to provide a metal nanoparticle-containing dispersion composition in which the dispersibility of metal nanoparticles in fluorine-based solvents is improved.
  • the inventors of the present disclosure have made intensive studies to solve the above problems, and as a result, in a dispersion composition containing surface-modified metal nanoparticles coated with a protective agent, a fluorine-based solvent, and a fluorine-based dispersant, metal nanoparticles
  • a dispersion composition containing surface-modified metal nanoparticles coated with a protective agent, a fluorine-based solvent, and a fluorine-based dispersant metal nanoparticles
  • the present disclosure provides a metal nanoparticle-containing dispersion composition containing surface-modified metal nanoparticles having a structure in which the surfaces of the metal nanoparticles are coated with a protective agent, a fluorine-based solvent, and a fluorine-based dispersant. .
  • the protective agent is preferably a compound having at least one reactive group selected from the group consisting of carboxyl group, hydroxyl group, amino group, sulfo group and thiol group.
  • the average primary particle size of the surface-modified metal nanoparticles is preferably 300 nm or less.
  • the fluorine-based dispersant is preferably a fluorine-based silane compound.
  • the present disclosure also provides a coating agent containing the metal nanoparticle-containing dispersion composition.
  • the present disclosure also provides an article having a base material and a coating layer formed from the coating agent on the surface of the base material.
  • the dispersibility of metal nanoparticles in fluorine-based solvents is improved. Therefore, it is possible to form a coating layer uniformly containing metal nanoparticles on a substrate such as glass by using a coating agent containing this.
  • the metal nanoparticle-containing dispersion composition of the present disclosure is characterized by containing surface-modified metal nanoparticles having a structure in which the surface of the metal nanoparticles is coated with a protective agent, a fluorine-based solvent, and a fluorine-based dispersant. .
  • the surface-modified metal nanoparticles of the present disclosure have a structure in which the particle surface is coated with an organic protective agent.
  • the volume-based average primary particle diameter (median diameter, D 50 ) of the surface-modified metal nanoparticles is preferably 300 nm or less, more preferably 100 nm or less, and still more preferably 80 nm or less from the viewpoint of the appearance and visibility of the coating layer. , and particularly preferably 50 nm or less. Although the lower limit is not particularly limited, it is, for example, 1.0 nm.
  • the average primary particle size of the surface-modified metal nanoparticles can be measured, for example, by a dynamic light scattering method (Doppler scattering can be measured by optical analysis).
  • metal nanoparticles examples include gold, silver, copper, nickel, palladium, tin, aluminum, and alloys thereof. Among them, copper and silver are preferred, and silver is more preferred.
  • the metal nanoparticles may be made of a single metal, or may be made of two or more metals such as a core-shell structure. These may use only 1 type and may use 2 or more types.
  • the metal nanoparticles may be spherical, amorphous, flake (flat), or any other shape, with spherical or irregular shapes being preferred. These may use only 1 type and may use 2 or more types.
  • the organic protective agent for example, a compound having at least one reactive group selected from the group consisting of a carboxyl group, a hydroxyl group, an amino group, a sulfo group and a thiol group, or a high molecular weight compound having the reactive group
  • examples include molecules (polyvinylpyrrolidone, polyether, polyethyleneimine, polyacrylic acid, polyacrylamide, polyvinyl alcohol, polyethylene glycol, polyethylene oxide, etc.), among which compounds having an amino group are preferred.
  • the number of carbon atoms in the above compound is preferably 4 to 18. That is, the organic protective agent is preferably a compound having 4 to 18 carbon atoms and having an amino group (amine having 4 to 18 carbon atoms).
  • Examples of the amine include a monoamine compound having one amino group or a polyvalent amine compound (diamine compound, etc.) having two or more of at least one amino group selected from an amino group, a monosubstituted amino group, and a disubstituted amino group. is mentioned.
  • the amine preferably contains at least one selected from monoamine (1) having a total carbon number of 6 or more, monoamine (2) having a total carbon number of 5 or less, and diamine (3) having a total carbon number of 8 or less. .
  • the above monoamine (1) is an amine compound having a linear alkyl group with a total carbon number of 6 to 18 (more preferably 6 to 16, still more preferably 6 to 12) from the viewpoint that metal nanoparticles are less likely to aggregate.
  • Examples include hexylamine, heptylamine, octylamine, nonylamine, decylamine, undecylamine, dodecylamine, tridecylamine, tetradecylamine, pentadecylamine, hexadecylamine, heptadecylamine, and octadecylamine. be done.
  • an amine having a branched alkyl group having a total carbon number of 6 to 16 (more preferably 6 to 10) is used because it becomes easier to disperse even in a small amount due to steric factors. It may be a compound such as isohexylamine, 2-ethylhexylamine, tert-octylamine, and the like.
  • the above-mentioned monoamine (1) also includes, for example, primary amines having a cycloalkyl group (such as cyclohexylamine), primary amines having an alkenyl group (such as oleylamine), and secondary amines having a linear alkyl group.
  • primary amines having a cycloalkyl group such as cyclohexylamine
  • primary amines having an alkenyl group such as oleylamine
  • secondary amines having a linear alkyl group such as cycloalkyl group
  • Amines N,N-dipropylamine, N,N-dibutylamine, N,N-dipentylamine, N,N-dihexylamine, N,N-dipeptylamine, N,N-dioctylamine, N,N-dinonylamine, N,N-didecylamine, N,N-diundecylamine, N,N-didodecylamine, N-propyl-N-butylamine, etc.), secondary amines having branched alkyl groups (N,N-diiso hexylamine, N,N-di(2-ethylhexyl)amine, etc.), tertiary amines having a linear alkyl group (tributylamine, trihexylamine, etc.), tertiary amines having a branched alkyl group ( triisohexylamine, tri(2-ethylhexyl)
  • the monoamine (2) has a linear or branched alkyl group having a total carbon number of 2 to 5 (more preferably 3 to 5, still more preferably 4 to 5) from the viewpoint of having high coordinating ability. Amine compounds are preferred.
  • the monoamine (2) include primary amines having a linear or branched alkyl group (ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, sec-butylamine, tert-butylamine, pentylamine, isopentylamine, tert-pentylamine, etc.), secondary amines having linear or branched alkyl groups (N,N-dimethylamine, N,N-diethylamine, N-methyl -N-propylamine, N-ethyl-N-propylamine, etc.).
  • primary amines having a linear or branched alkyl group ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, sec-butylamine, tert-butylamine, pentylamine, isopentylamine, tert-penty
  • a diamine having an amino group and a disubstituted amino group is preferable because the two amino groups have different coordinating abilities and the coordination is unlikely to be complicated.
  • N,N-dimethylethylenediamine. N,N-diethylethylenediamine, N,N-dimethyl-1,3-propanediamine, N,N-diethyl-1,3-propanediamine, N,N-dimethyl-1,4-butanediamine, N,N -diethyl-1,4-butanediamine, N,N-dimethyl-1,6-hexanediamine, and the like.
  • the diamine (3) is a diamine having two amino groups (ethylenediamine, 1,3-propanediamine, 2,2-dimethyl-1,3-propanediamine, 1,4-butanediamine, 1,5-pentanediamine , 1,6-hexanediamine, 1,7-heptanediamine, 1,8-octanediamine, 1,5-diamino-2-methylpentane, etc.), diamines having two monosubstituted amino groups (N,N'- Dimethylethylenediamine, N,N'-diethylethylenediamine, N,N'-dimethyl-1,3-propanediamine, N,N'-diethyl-1,3-propanediamine, N,N'-dimethyl-1,4- butanediamine, N,N'-diethyl-1,4-butanediamine, N,N'-dimethyl-1,6-hexanediamine, etc.).
  • Only one kind of the monoamine (1), the monoamine (2) and the diamine (3) may be used, or two or more kinds thereof may be used.
  • the amine may contain other amine compounds in addition to the monoamine (1), the monoamine (2) and the diamine (3), but the content of the other amine compounds in the amine is , the monoamine (1), the monoamine (2), the diamine (3), and the other amine compound are preferably 40.0% by weight or less, more preferably 20.0% by weight, based on the total 100% by weight. Below, more preferably 10.0% by weight or less, particularly preferably 0% by weight.
  • the surface-modified metal nanoparticles can be produced, for example, by mixing the metal compound and the organic protective agent to form a complex, and thermally decomposing the resulting complex.
  • metal compounds examples include metal carboxylates (metal formates, metal acetates, metal oxalates, metal malonates, metal benzoates, metal phthalates, etc.), metal halides (metal fluorides , metal chlorides, metal bromides, metal iodides, etc.), metal inorganic acid salts (metal sulfates, metal nitrates, metal carbonates, etc.) can be used.
  • metal carboxylates metal formates, metal acetates, metal oxalates, metal malonates, metal benzoates, metal phthalates, etc.
  • metal halides metal fluorides , metal chlorides, metal bromides, metal iodides, etc.
  • metal inorganic acid salts metal sulfates, metal nitrates, metal carbonates, etc.
  • metal oxalates are preferable because they easily generate metals by decomposition and are less likely to produce impurities other than metals.
  • the amount of the organic protective agent (preferably the amine) used is preferably 1 to 50 mol with respect to 1 mol of the metal atom of the metal compound, in terms of imparting sufficient dispersibility to the surface-modified metal nanoparticles. , more preferably 10 to 40 mol, still more preferably 15 to 35 mol.
  • the reaction between the metal compound and the organic protective agent for forming the complex may be carried out in the presence of a reaction solvent or in the absence of a reaction solvent.
  • a reaction solvent for example, an alcohol solvent (preferably an aliphatic alcohol) having 3 or more carbon atoms can be used.
  • the amount of the reaction solvent used is preferably 120 to 1000 parts by weight, more preferably 130 to 800 parts by weight, still more preferably 150 to 500 parts by weight, based on 100 parts by weight of the metal compound.
  • the reaction to generate the above complex can be carried out, for example, at a reaction temperature of 5 to 40°C and a reaction time of 30 minutes to 3 hours.
  • the above thermal decomposition may be carried out in the presence of a reaction solvent similar to the above reaction solvent.
  • the thermal decomposition temperature is, for example, preferably 80 to 120° C., more preferably 100 to 110° C.
  • the thermal decomposition time is, for example, 10 minutes to 5 hours.
  • the thermal decomposition of the complex can be carried out in an air atmosphere or an inert gas (nitrogen, argon, etc.) atmosphere.
  • the surface-modified metal nanoparticles obtained by the thermal decomposition may be washed by centrifugation or decantation.
  • the content of the organic protective agent in the surface-modified metal nanoparticles is preferably 0.5 to 10.0% by weight, more preferably 1.0 to 7%, based on 100% by weight of the surface-modified metal nanoparticles. 0% by weight, more preferably 1.5 to 5.0% by weight. When the content of the organic protective agent is within the above range, the surface-modified metal nanoparticles are easily dispersed uniformly.
  • the metal nanoparticle-containing dispersion composition of the present disclosure contains a fluorine-based solvent as a dispersion medium.
  • the fluorinated solvent is not particularly limited, but examples thereof include fluorinated aromatic hydrocarbon solvents, fluorinated hydrocarbon solvents, and fluorinated ether solvents.
  • fluorine-containing aromatic hydrocarbon solvent examples include 1,3-bis(trifluoromethyl)benzene, trifluorotoluene, octafluorotoluene, hexafluorobenzene and the like.
  • fluorine-containing hydrocarbon solvent examples include perfluoropentane, perfluorohexane, perfluoroheptane, perfluorooctane, perfluorononane, perfluorodecane, perfluoromethylcyclohexane, octafluorocyclopentene, perfluorodecalin, perfluorodecane, Fluoro(1,3-dimethylcyclohexane), 1,1,2,2,3,3,4-heptafluorocyclopentane, 1,1,1,2,3,4,4,5,5,5-deca fluoropentane, 1,1,1,2,2,3,3,4,4,5,5,6,6-tridecafluorooctane and the like.
  • fluorine-containing ether solvent examples include hexafluoroisopropyl methyl ether, perfluoro(2-butyltetrahydrofuran), perfluoropolyether, methyl nonafluorobutyl ether, methyl nonafluoroisobutyl ether, ethyl nonafluorobutyl ether, ethyl nonafluoro isobutyl ether, 1,1,1,2,3,4,4,5,5,5-decafluoro-3-methoxy-2-(trifluoromethyl)pentane, 1,1,1,2,2,3 , 4,4,5,5,6,6,6-tridecafluoro-3-methoxypentane, etc.).
  • Only one type of the fluorine-based solvent may be used, or two or more types may be used.
  • the metal nanoparticle-containing dispersion composition of the present disclosure may contain other types of solvents within a range that does not impair the effect.
  • the fluorine-based dispersant according to the present disclosure is a fluorine-containing compound having a non-reactive fluorine-containing organic group and a reactive group in one molecule, and is adsorbed or bonded to the metal surface of the metal nanoparticles by the reactive group. Then, the surface-modified metal nanoparticles are uniformly dispersed in the fluorine-based solvent by having an affinity with the fluorine-based solvent due to the fluorine organic group.
  • the fluorine-based dispersant differs from the organic protective agent in that it has fluorine in its structure.
  • Examples of the fluorine-containing organic group possessed by the fluorine-based dispersant include groups containing a fluoroalkyl group, a fluoroaryl group, and the like.
  • the fluoroalkyl group is a linear or branched alkyl group in which some or all of the hydrogen atoms are replaced with fluorine atoms
  • the fluoroaryl group is an aryl group in which part of the hydrogen atoms are Alternatively, all of them are substituted with fluorine atoms.
  • the fluorine-containing organic group may be a group in which a fluoroalkyloxy group or a fluoroaryloxy group and one or more alkyleneoxy groups are connected via an oxygen atom.
  • the fluoroalkyloxy group is a linear or branched alkyloxy group in which some or all of the hydrogen atoms are replaced with fluorine atoms. Some or all of the atoms are replaced with fluorine atoms, and the above alkyleneoxy group is a linear or branched alkyleneoxy group in which some or all of the hydrogen atoms are replaced with fluorine atoms. be.
  • Examples of reactive groups possessed by the fluorine-containing compound include carboxyl groups, amino groups, thiol groups, hydroxyl groups, sulfo groups, phosphono groups, ester groups, amide groups, hydrolyzable silyl groups, and the like.
  • a hydrolyzable silyl group is preferred because it facilitates obtaining stable dispersibility of the metal nanoparticles.
  • fluorine-containing compound having a carboxyl group examples include 2,3,4,5,6-pentafluorobenzoic acid, 2,3,4,6-tetrafluorobenzoic acid, 2,4,5- trifluorobenzoic acid, 2,3,4-trifluorobenzoic acid, 2-ethyl-tetrafluorobenzoic acid, 2-isopropyl-tetrafluorobenzoic acid, 3-cyclopropyl-2,4,5-trifluorobenzoic acid, 2-butyl-tetrafluorobenzoic acid, undecafluorohexanoic acid, nonadecafluorodecanoic acid and the like.
  • fluorine-containing compound having an amino group examples include 2,3,4,5,6-pentafluoroaniline, 2,3,4,5-tetrafluoroaniline, 2,4,5-trifluoro Phenylamine, 4,5-difluoro-2-aminobenzotrifluoride, 2-amino-5,6-difluoro-benzotrifluoride, (3,4,5-trifluorophenyl)-(7-methoxymethyl-[1 ,4]-dioxano[2,3-g]quinazolin-4-yl)-amine, 4-fluoro-2-(trifluoromethyl)-aniline, 3,4-difluoroaniline, 2-(difluoromethyl)-4 -fluoroaniline, 2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-pentadecafluorooctan-1-amine and the like.
  • fluorine-containing compound having a thiol group examples include 4-trifluoromethylbenzenethiol, 3-trifluoromethylbenzenethiol, pentafluorobenzenethiol, 2,3,5,6-tetrafluorobenzenethiol, 2,3,5,6-tetrafluoro-4-(trifluoromethyl)benzenethiol, 2,3,5,6-tetrafluoro-4-mercaptobenzoic acid methyl ester, 3,5-bistrifluoromethylbenzenethiol, 4-fluorobenzenethiol and 11-(2,3,4,5,6-pentafluorobenzyloxy)-1-undecanethiol (chemical formula below), 1H,1H,2H,2H-perfluorodecanethiol, 1H,1H , 2H,2H-perfluorooctanethiol and the like.
  • the fluorine-containing silane compound according to the present disclosure is a fluorine-containing compound having the hydrolyzable silyl group, and is represented by the following formula (1), for example.
  • R represents a fluoroalkyl group or a fluorine-containing organic group having a fluoroalkyloxy group and a fluoroalkyleneoxy group; -4 alkoxy group, aryloxy group having 6 to 10 carbon atoms, or acyloxy group having 1 to 4 carbon atoms, and Y is the same or different, an alkyl group having 1 to 10 carbon atoms, or an alkyl group having 1 to 10 carbon atoms It represents 3-10 cycloalkyl groups.
  • n is an integer of 1-3.
  • the number of carbon atoms in R is preferably 5 to 300, more preferably 10 to 200, still more preferably 15 to 150.
  • n is preferably 2 or 3, more preferably 3, from the viewpoint of easily obtaining stable dispersibility.
  • the halogen atom for X above includes a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • alkoxy group for X examples include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy and tert-butoxy groups.
  • Examples of the aryloxy group for X include a phenoxy group.
  • acyloxy group for X examples include an acetyloxy group, a propynyloxy group, and a pivaloyloxy group.
  • the above X is preferably an alkoxy group, more preferably a methoxy group or an ethoxy group.
  • alkyl group for Y examples include methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, isobutyl group, tert-butyl group and the like, and the cycloalkyl group for Y above. Examples include cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group and the like.
  • fluorine-based silane compound examples include (heptadecafluoro-1,1,2,2-tetrahydrodecyl)-triethoxysilane and (heptadecafluoro-1,1,2,2-tetrahydrodecyl).
  • fluorine-based silane compound is the trade name "OPTOOL HD-1100TH” (manufactured by Daikin Industries, Ltd.).
  • fluorine-based dispersant Only one type of the fluorine-based dispersant may be used, or two or more types may be used.
  • the content of the fluorine-based dispersant in the metal nanoparticle-containing dispersion composition of the present disclosure is preferably 0.001% by weight or more with respect to 100% by weight of the metal nanoparticle-containing dispersion composition of the present disclosure, More preferably 0.001 to 10.0 wt%, still more preferably 0.005 to 7.0 wt%, particularly preferably 0.010 to 5.0 wt%, most preferably 0.05 to 3.0 wt% %.
  • the content of the fluorine-based dispersant is within the above range, it becomes easier to maintain a uniform dispersed state.
  • the content of the fluorine-based dispersant in the metal nanoparticle-containing dispersion composition of the present disclosure is preferably 0.1 parts by weight or more, more preferably 100 parts by weight of the metal nanoparticles of the present disclosure. 0.1 to 1000 parts by weight, more preferably 0.5 to 500 parts by weight, particularly preferably 1.0 to 200 parts by weight.
  • the metal nanoparticle-containing dispersion composition of the present disclosure can be produced by mixing the metal nanoparticles, the fluorine-based solvent, and the fluorine-based dispersant.
  • generally known mixing equipment such as a revolution-type stirring and degassing device, a homogenizer, a planetary mixer, a three-roll mill, and a bead mill can be used. Each component may be mixed simultaneously or sequentially.
  • the metal nanoparticle-containing dispersion composition of the present disclosure can stably maintain the dispersibility of the metal nanoparticles over a long period of time, it can be suitably used, for example, as a coating agent or as a raw material for a coating agent. can be done.
  • the coating agent of the present disclosure contains the metal nanoparticle-containing dispersion composition of the present disclosure.
  • the metal nanoparticle-containing dispersion composition contained in the coating agent of the present disclosure may be diluted with a solvent containing the fluorine-based solvent.
  • the content of the metal nanoparticles in the coating agent of the present disclosure is, for example, preferably 0.001 to 10.0 wt%, more preferably 0.002 to 8, relative to 100 wt% of the coating agent of the present disclosure. 0% by weight, more preferably 0.005 to 5.0% by weight.
  • the fluorine-containing compound may be added as appropriate.
  • the coating agent of the present disclosure may also contain a coating film-forming component that is soluble in fluorine-based solvents.
  • the coating film-forming component include amorphous or crystalline fluorine-containing polymers (polyperfluorobutenyl vinyl ether, tetrafluoroethylene/perfluoro(butenyl vinyl ether) copolymer, tetrafluoroethylene/perfluoro ( propenyl vinyl ether) copolymer, tetrafluoroethylene/perfluoro-2,2-dimethyl-1,3-dioxole copolymer, tetrafluoroethylene/hexafluoropropylene copolymer, hexafluoropropylene/vinylidene fluoride copolymer , tetrafluoroethylene/perfluoromethyl vinyl ether copolymer, tetrafluoroethylene/perfluoropropyl vinyl ether copolymer, etc.) and
  • the total content of the fluorine-based dispersant and the coating film-forming component in the metal nanoparticle-containing dispersion composition of the present disclosure is 0.1 parts by weight or more with respect to 100 parts by weight of the surface-modified metal nanoparticles. is preferred, more preferably 0.1 to 200 parts by weight, still more preferably 0.5 to 150 parts by weight, particularly preferably 1.0 to 100 parts by weight.
  • a coating layer can be formed on the substrate surface by applying the coating agent of the present disclosure to the surface of a substrate (transparent plastic, glass, etc.), drying, and solidifying.
  • Examples of articles having the base material and the coating layer include optical recording media (magneto-optical discs, optical discs, etc.), optical components (lenses, prisms, pellicles, polarizing plates, optical filters, mirrors, lamp covers, light covers, etc.), various screen display devices (televisions, PC monitors, mobile phones, game consoles, digital cameras, cash dispensers, car navigation devices, etc.), protective glass (show windows, showcases, etc.), vehicles (vehicles, window glass of trains, aircraft, ships, etc.).
  • Silver oxalate (molecular weight: 303.78) was obtained from silver nitrate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) and oxalic acid dihydrate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.). A 100 mL flask was charged with 3.0 g (9.9 mmol) of this silver oxalate, and 4.5 g of n-butanol was added thereto to prepare an n-butanol slurry of silver oxalate.
  • the temperature of the reaction solution is raised from 30° C. to 100° C., and then heated for 1 hour while maintaining the temperature at 100° C. to thermally decompose the silver oxalate-amine complex. , a suspension of dark blue surface-modified silver nanoparticles in the amine mixture was obtained.
  • a liquid composition in which a mixed solvent of n-butanol/n-octane (weight ratio 70/30) is added to and mixed with the surface-modified silver nanoparticles in a wet state so that the content of the surface-modified silver nanoparticles is 50% by weight. prepared the product.
  • the surface-modified silver nanoparticles, fluorine-based solvents, fluorine-based dispersants, and fluorine-free dispersants used in Examples and Comparative Examples are as follows.
  • ⁇ HD-TH Fluorinated solvent, trade name “Optool HD-TH”, manufactured by Daikin Industries, Ltd.
  • ⁇ Perfluorohexane trade name “Tetradecafluorohexane”, manufactured by Tokyo Chemical Industry Co., Ltd.
  • Disposant containing no fluorine ⁇ DisperBYK106: Salt of polymer compound having acid group, manufactured by BYK-Chemie Japan Co., Ltd.
  • DisposerBYK180 Alkylolammonium salt of copolymer having acid group, manufactured by BYK-Chemie Japan Co., Ltd.
  • Example 1 Silver nanoparticle undiluted solution (0.1 g) and HD-1100TH (4.9 g) were weighed into a Teflon (registered trademark) container and stirred and mixed so that the content (% by weight) shown in Table 1 below was obtained. An evaluation sample of the nanoparticle dispersion was prepared. When the evaluation sample was filtered using a syringe filter (DISMIC-25CS045AN), a yellow transparent liquid was obtained.
  • a syringe filter DISMIC-25CS045AN
  • Example 2 An evaluation sample was prepared in the same manner as in Example 1 except that the content (% by weight) shown in Table 1 below was blended. When the evaluation sample was filtered with a syringe filter, a yellow transparent liquid was obtained as in Example 1.
  • Example 3 An evaluation sample was prepared in the same manner as in Example 1 except that the content (% by weight) shown in Table 1 below was blended. When the evaluation sample was filtered with a syringe filter, a black transparent liquid was obtained.
  • Example 4 An evaluation sample was prepared in the same manner as in Example 1 except that after concentrating HD-1100TH 10 times, it was blended so that the content (% by weight) shown in Table 1 below was obtained. When the evaluation sample was filtered with a syringe filter, a yellow transparent liquid was obtained as in Example 1.
  • [Appendix 1] A metal nanoparticle-containing dispersion liquid composition containing surface-modified metal nanoparticles having a structure in which the surfaces of the metal nanoparticles are coated with a protective agent, a fluorine-based solvent, and a fluorine-based dispersant.
  • the protective agent is a compound having at least one reactive group selected from the group consisting of a carboxyl group, a hydroxyl group, an amino group, a sulfo group and a thiol group.
  • a particle-containing dispersion composition is a compound having at least one reactive group selected from the group consisting of a carboxyl group, a hydroxyl group, an amino group, a sulfo group and a thiol group.
  • [Appendix 3] The metal nanoparticle-containing dispersion composition according to Appendix 1, wherein the protective agent is an amine having 4 to 18 carbon atoms.
  • the protective agent is a monoamine having a linear or branched alkyl group with a total carbon number of 2 to 5 (preferably 3 to 5, more preferably 4 to 5).
  • Appendix 5 The metal nanoparticle-containing dispersion composition according to Appendix 1, wherein the protective agent is n-butylamine.
  • Appendix 8 Any of Appendices 1 to 6, wherein the average primary particle size of the surface-modified metal nanoparticles is 1.0 nm or more and 300 nm or less (preferably 100 nm or less, more preferably 80 nm or less, and still more preferably 50 nm or less). or the metal nanoparticle-containing dispersion composition according to any one of the above.
  • the content of the organic protective agent is 0.5 to 10.0 wt% (preferably 1.0 to 7.0 wt%, more preferably is 1.5 to 5.0% by weight), the metal nanoparticle-containing dispersion composition according to any one of appendices 1 to 8.
  • Appendix 10 Any of Appendices 1 to 9, wherein the fluorine-based solvent is at least one selected from the group consisting of a fluorine-containing aromatic hydrocarbon solvent, a fluorine-containing hydrocarbon solvent, and a fluorine-containing ether solvent. or the metal nanoparticle-containing dispersion composition according to any one of the above.
  • the fluorine-based solvent is at least one selected from the group consisting of a fluorine-containing aromatic hydrocarbon solvent, a fluorine-containing hydrocarbon solvent, and a fluorine-containing ether solvent. or the metal nanoparticle-containing dispersion composition according to any one of the above.
  • the fluorine-based solvent is perfluoropentane, perfluorohexane, perfluoroheptane, perfluorooctane, perfluorononane, perfluorodecane, perfluoromethylcyclohexane, octafluorocyclopentene, perfluorodecalin, perfluoro ( 1,3-dimethylcyclohexane), 1,1,2,2,3,3,4-heptafluorocyclopentane, 1,1,1,2,3,4,4,5,5,5-decafluoropentane , and at least one selected from the group consisting of 1,1,1,2,2,3,3,4,4,5,5,6,6-tridecafluorooctane, Appendices 1 to 9 Metal nanoparticle-containing dispersion liquid composition according to any one of.
  • the fluorine-containing dispersant is a fluorine-containing compound having a non-reactive fluorine-containing organic group and a reactive group in one molecule, and the fluorine-containing organic group is a fluoroalkyl group and/or a fluoro
  • the metal nanoparticle-containing dispersion composition according to any one of Appendices 1 to 11, which is a group containing an aryl group.
  • the reactive group is at least one selected from the group consisting of a carboxyl group, an amino group, a thiol group, a hydroxyl group, a sulfo group, a phosphono group, an ester group, an amide group and a hydrolyzable silyl group.
  • the metal nanoparticle-containing dispersion composition according to any one of Appendices 1 to 11, wherein the fluorine-based dispersant is a fluorine-based silane compound represented by the following formula (1).
  • R represents a fluoroalkyl group, or a fluorine-containing organic group having a fluoroalkyloxy group and a fluoroalkyleneoxy group
  • X is the same or different, a hydrogen atom, a halogen atom, a carbon number an alkoxy group having 1 to 4 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, or an acyloxy group having 1 to 4 carbon atoms
  • Y is the same or different, an alkyl group having 1 to 10 carbon atoms, or carbon represents a cycloalkyl group of numbers 3 to 10.
  • n is an integer of 1 to 3)
  • the content of the fluorine-based dispersant is 0.001% by weight or more (preferably 0.001 to 10.0% by weight, more than Preferably 0.005 to 7.0% by weight, more preferably 0.010 to 5.0% by weight, particularly preferably 0.05 to 3.0% by weight), any one of appendices 1 to 15
  • the content of the fluorine-based dispersant is 0.1 parts by weight or more (preferably 0.1 to 1000 parts by weight, more preferably 0.5 to 500 parts by weight with respect to 100 parts by weight of the metal nanoparticles Parts, more preferably 1.0 to 200 parts by weight, the metal nanoparticle-containing dispersion composition according to any one of Appendixes 1 to 16.
  • Appendix 18 A coating agent containing the metal nanoparticle-containing dispersion composition according to any one of Appendices 1 to 17.
  • the content of the metal nanoparticles is 0.001 to 10.0 wt% (preferably 0.002 to 8.0 wt%, more preferably 0.002 to 8.0 wt%, more preferably 0.001 to 10.0 wt% with respect to 100 wt% of the coating agent). 005 to 5.0% by weight), the coating agent according to Appendix 18.
  • An article comprising a substrate and a coating layer formed from the coating agent according to Appendix 19 on the surface of the substrate.
  • the dispersibility of the metal nanoparticles in fluorine-based solvents is improved.
  • a uniform coating layer can be formed. Therefore, the present disclosure has industrial applicability.

Abstract

The present invention provides a metal nanoparticle-containing dispersion composition in which metal nanoparticles are uniformly dispersed in a fluorine-based solvent.　The metal nanoparticle-containing dispersion composition of the present disclosure contains a fluorine-based solvent, a fluorine-based dispersant, and metal nanoparticles coated with a protective agent. The coating agent of the present disclosure contains the metal nanoparticle-containing dispersion composition. The article of the present disclosure has a substrate and a coating layer formed on the substrate surface from the coating agent according to claim 7.

Description

金属ナノ粒子含有分散液組成物Dispersion composition containing metal nanoparticles
　本開示は、金属ナノ粒子含有分散液組成物に関する。本願は、２０２１年３月９日に日本に出願した、特願２０２１－０３７１２７号の優先権を主張し、その内容をここに援用する。 The present disclosure relates to a metal nanoparticle-containing dispersion liquid composition. This application claims priority from Japanese Patent Application No. 2021-037127 filed in Japan on March 9, 2021, the content of which is incorporated herein.
　従来から、ガラス等の透明部材について、肌の接触による皮脂等汚れの付着や降雨等による水滴の付着等によって外観や視認性が損なわれやすいことから、撥水撥油性による防汚性や汚れの落ち易さ等を付与するために、含フッ素コーティング剤等による表面処理が行われている。 Conventionally, transparent materials such as glass tend to lose their appearance and visibility due to the adhesion of dirt such as sebum due to contact with the skin and the adhesion of water droplets due to rainfall. In order to impart ease of removal, etc., the surface is treated with a fluorine-containing coating agent or the like.
　中でも、タッチパネル化されたディスプレイについては、視認性や操作性が重要であることから特に高い防汚性及び汚れ落ちが求められることに加えて、直接触れて操作することから、清潔さや衛生面に関する抗菌性を有することも併せて望まれている。 In particular, for touch panel displays, visibility and operability are important, so in addition to being required to have particularly high antifouling properties and dirt removal, they are operated by direct touch, so cleanliness and hygiene are required. It is also desired to have antibacterial properties.
　抗菌性を付与するためには銀ナノ粒子等の金属ナノ粒子を利用することができる一方で、コーティング剤は溶液や分散液等の液状組成物である。そして、金属ナノ粒子を液状組成物中に良好に分散させるために様々な検討がされており、例えば、特許文献１には、特定の銀化合物と特定のアミン類とを反応させた錯体を熱分解することによって得られる銀ナノ粒子を、アルコール系溶剤に分散させた銀ナノ粒子含有分散液が開示されている。 While metal nanoparticles such as silver nanoparticles can be used to impart antibacterial properties, coating agents are liquid compositions such as solutions and dispersions. Various studies have been made to disperse metal nanoparticles well in a liquid composition. A silver nanoparticle-containing dispersion is disclosed in which silver nanoparticles obtained by decomposition are dispersed in an alcoholic solvent.
国際公開２０１５／０６００８４号公報International Publication No. 2015/060084
　しかし、特許文献１の分散液に係る金属ナノ粒子では、含フッ素コーティング剤に配合されるフッ素系溶剤に対して分散性が劣るため、フッ素系溶剤を用いて均一な分散液を得ることが困難であるという問題があった。 However, since the metal nanoparticles in the dispersion of Patent Document 1 are inferior in dispersibility to the fluorine-based solvent blended in the fluorine-containing coating agent, it is difficult to obtain a uniform dispersion using the fluorine-based solvent. There was a problem that
　従って、本開示の目的は、金属ナノ粒子のフッ素系溶剤に対する分散性が向上した金属ナノ粒子含有分散液組成物を提供することにある。 Therefore, an object of the present disclosure is to provide a metal nanoparticle-containing dispersion composition in which the dispersibility of metal nanoparticles in fluorine-based solvents is improved.
　本開示の発明者は上記課題を解決するため鋭意検討した結果、保護剤で被覆された表面修飾金属ナノ粒子、フッ素系溶剤及びフッ素系分散剤を含有する分散液組成物において、金属ナノ粒子の均一な分散性が達成されることを見いだし、本開示を完成させるに至った。 The inventors of the present disclosure have made intensive studies to solve the above problems, and as a result, in a dispersion composition containing surface-modified metal nanoparticles coated with a protective agent, a fluorine-based solvent, and a fluorine-based dispersant, metal nanoparticles The discovery that uniform dispersion is achieved has led to the completion of the present disclosure.
　すなわち、本開示は、金属ナノ粒子の表面が保護剤で被覆された構成を有する表面修飾金属ナノ粒子、フッ素系溶剤及びフッ素系分散剤を含有する、金属ナノ粒子含有分散液組成物を提供する。 That is, the present disclosure provides a metal nanoparticle-containing dispersion composition containing surface-modified metal nanoparticles having a structure in which the surfaces of the metal nanoparticles are coated with a protective agent, a fluorine-based solvent, and a fluorine-based dispersant. .
　上記保護剤は、カルボキシル基、ヒドロキシル基、アミノ基、スルホ基及びチオール基からなる群より選択される少なくとも１種の反応性基を有する化合物であることが好ましい The protective agent is preferably a compound having at least one reactive group selected from the group consisting of carboxyl group, hydroxyl group, amino group, sulfo group and thiol group.
　上記表面修飾金属ナノ粒子の平均一次粒子径は、３００ｎｍ以下であることが好ましい。 The average primary particle size of the surface-modified metal nanoparticles is preferably 300 nm or less.
　上記フッ素系分散剤は、フッ素系シラン化合物であることが好ましい。 The fluorine-based dispersant is preferably a fluorine-based silane compound.
　本開示は、また、上記金属ナノ粒子含有分散液組成物を含有する、コーティング剤を提供する。 The present disclosure also provides a coating agent containing the metal nanoparticle-containing dispersion composition.
　本開示は、また、基材と、該基材表面に上記コーティング剤から形成されるコーティング層とを有する物品を提供する。 The present disclosure also provides an article having a base material and a coating layer formed from the coating agent on the surface of the base material.
　本開示の金属ナノ粒子含有分散液組成物では、金属ナノ粒子のフッ素系溶剤に対する分散性が向上する。そのため、これを含有するコーティング剤を用いて、ガラス等の基材上に、金属ナノ粒子を均一に含むコーティング層を形成することができる。 In the metal nanoparticle-containing dispersion composition of the present disclosure, the dispersibility of metal nanoparticles in fluorine-based solvents is improved. Therefore, it is possible to form a coating layer uniformly containing metal nanoparticles on a substrate such as glass by using a coating agent containing this.
［金属ナノ粒子含有分散液組成物］
　本開示の金属ナノ粒子含有分散液組成物は、金属ナノ粒子の表面が保護剤で被覆された構成を有する表面修飾金属ナノ粒子、フッ素系溶剤及びフッ素系分散剤を含有することを特徴とする。 [Metal Nanoparticle-Containing Dispersion Composition]
The metal nanoparticle-containing dispersion composition of the present disclosure is characterized by containing surface-modified metal nanoparticles having a structure in which the surface of the metal nanoparticles is coated with a protective agent, a fluorine-based solvent, and a fluorine-based dispersant. .
＜表面修飾金属ナノ粒子＞
　本開示の表面修飾金属ナノ粒子は、粒子表面を有機保護剤によって被覆された構成を有する。 <Surface modified metal nanoparticles>
The surface-modified metal nanoparticles of the present disclosure have a structure in which the particle surface is coated with an organic protective agent.
　上記表面修飾金属ナノ粒子の体積基準の平均一次粒子径（メディアン径、Ｄ50）は、コーティング層の外観や視認性の点から、３００ｎｍ以下が好ましく、より好ましくは１００ｎｍ以下、更に好ましくは８０ｎｍ以下、特に好ましくは５０ｎｍ以下である。下限は、特に限定されないが、例えば、１．０ｎｍである。なお、表面修飾金属ナノ粒子の平均一次粒子径は、例えば、市販の動的光散乱式粒径分布測定装置（Ｍａｌｖｅｒｎ Ｐａｎａｌｙｔｉｃａｌ社製、Ｚｅｔａｓｉｚｅｒ Ｎａｎｏ ＺＳ等）を用いて動的光散乱法（ドップラー散乱光解析）により測定することができる。 The volume-based average primary particle diameter (median diameter, D 50 ) of the surface-modified metal nanoparticles is preferably 300 nm or less, more preferably 100 nm or less, and still more preferably 80 nm or less from the viewpoint of the appearance and visibility of the coating layer. , and particularly preferably 50 nm or less. Although the lower limit is not particularly limited, it is, for example, 1.0 nm. The average primary particle size of the surface-modified metal nanoparticles can be measured, for example, by a dynamic light scattering method (Doppler scattering can be measured by optical analysis).
　上記金属ナノ粒子の材質としては、例えば、金、銀、銅、ニッケル、パラジウム、スズ、アルミニウム又はこれらの合金等が挙げられ、中でも、銅、銀が好ましく、銀がより好ましい。金属ナノ粒子は、単一の金属により形成されていてもよく、例えばコアシェル構造のように２種以上の金属により形成されていてもよい。これらは１種のみを用いてもよく、２種以上を用いてもよい。 Examples of materials for the metal nanoparticles include gold, silver, copper, nickel, palladium, tin, aluminum, and alloys thereof. Among them, copper and silver are preferred, and silver is more preferred. The metal nanoparticles may be made of a single metal, or may be made of two or more metals such as a core-shell structure. These may use only 1 type and may use 2 or more types.
　上記金属ナノ粒子は、球状、不定形状、フレーク状（扁平状）等、どのような形状であってよく、中でも、球状又は不定形状が好ましい。これらは１種のみを用いてもよく、２種以上を用いてもよい。 The metal nanoparticles may be spherical, amorphous, flake (flat), or any other shape, with spherical or irregular shapes being preferred. These may use only 1 type and may use 2 or more types.
　上記有機保護剤としては、例えば、カルボキシル基、ヒドロキシル基、アミノ基、スルホ基及びチオール基からなる群より選択される少なくとも１種の反応性基を有する化合物、又は、上記反応性基を有する高分子（ポリビニルピロリドン、ポリエーテル、ポリエチレンイミン、ポリアクリル酸、ポリアクリルアミド、ポリビニルアルコール、ポリエチレングリコール、ポリエチレンオキシド等）等が挙げられ、中でも、アミノ基を有する化合物が好ましい。また、上記化合物の炭素数は４～１８であることが好ましい。すなわち、上記有機保護剤は、アミノ基を有する炭素数４～１８の化合物（炭素数４～１８のアミン）であることが好ましい。 As the organic protective agent, for example, a compound having at least one reactive group selected from the group consisting of a carboxyl group, a hydroxyl group, an amino group, a sulfo group and a thiol group, or a high molecular weight compound having the reactive group Examples include molecules (polyvinylpyrrolidone, polyether, polyethyleneimine, polyacrylic acid, polyacrylamide, polyvinyl alcohol, polyethylene glycol, polyethylene oxide, etc.), among which compounds having an amino group are preferred. Further, the number of carbon atoms in the above compound is preferably 4 to 18. That is, the organic protective agent is preferably a compound having 4 to 18 carbon atoms and having an amino group (amine having 4 to 18 carbon atoms).
　上記アミンとしては、例えば、アミノ基、モノ置換アミノ基及びジ置換アミノ基から選択される少なくとも１種のアミノ基を、１つ有するモノアミン化合物又は２つ以上有する多価アミン化合物（ジアミン化合物等）が挙げられる。 Examples of the amine include a monoamine compound having one amino group or a polyvalent amine compound (diamine compound, etc.) having two or more of at least one amino group selected from an amino group, a monosubstituted amino group, and a disubstituted amino group. is mentioned.
　上記アミンは、総炭素数６以上のモノアミン（１）、総炭素数５以下のモノアミン（２）及び総炭素数が８以下のジアミン（３）から選択される少なくとも１種を含有することが好ましい。 The amine preferably contains at least one selected from monoamine (1) having a total carbon number of 6 or more, monoamine (2) having a total carbon number of 5 or less, and diamine (3) having a total carbon number of 8 or less. .
　上記モノアミン（１）としては、金属ナノ粒子が凝集しにくくなる点から、総炭素数６～１８（より好ましくは６～１６、更に好ましくは６～１２）の直鎖状アルキル基を有するアミン化合物が好ましく、例えば、ヘキシルアミン、ヘプチルアミン、オクチルアミン、ノニルアミン、デシルアミン、ウンデシルアミン、ドデシルアミン、トリデシルアミン、テトラデシルアミン、ペンタデシルアミン、ヘキサデシルアミン、ヘプタデシルアミン、オクタデシルアミン等が挙げられる。 The above monoamine (1) is an amine compound having a linear alkyl group with a total carbon number of 6 to 18 (more preferably 6 to 16, still more preferably 6 to 12) from the viewpoint that metal nanoparticles are less likely to aggregate. Examples include hexylamine, heptylamine, octylamine, nonylamine, decylamine, undecylamine, dodecylamine, tridecylamine, tetradecylamine, pentadecylamine, hexadecylamine, heptadecylamine, and octadecylamine. be done.
　また、上記モノアミン（１）としては、立体的因子により一層少量であっても分散しやすくなる点から、総炭素数６～１６（より好ましくは６～１０）の分岐鎖状アルキル基を有するアミン化合物であってもよく、例えば、イソヘキシルアミン、２－エチルヘキシルアミン、ｔｅｒｔ－オクチルアミン等が挙げられる。 In addition, as the monoamine (1), an amine having a branched alkyl group having a total carbon number of 6 to 16 (more preferably 6 to 10) is used because it becomes easier to disperse even in a small amount due to steric factors. It may be a compound such as isohexylamine, 2-ethylhexylamine, tert-octylamine, and the like.
　上記モノアミン（１）は、また、例えば、シクロアルキル基を有する第一級アミン（シクロヘキシルアミン等）、アルケニル基を有する第一級アミン等（オレイルアミン等）、直鎖状アルキル基を有する第二級アミン（Ｎ，Ｎ－ジプロピルアミン、Ｎ，Ｎ－ジブチルアミン、Ｎ，Ｎ－ジペンチルアミン、Ｎ，Ｎ－ジヘキシルアミン、Ｎ，Ｎ－ジペプチルアミン、Ｎ，Ｎ－ジオクチルアミン、Ｎ，Ｎ－ジノニルアミン、Ｎ，Ｎ－ジデシルアミン、Ｎ，Ｎ－ジウンデシルアミン、Ｎ，Ｎ－ジドデシルアミン、Ｎ－プロピル－Ｎ－ブチルアミン等）、分岐鎖状アルキル基を有する第二級アミン（Ｎ，Ｎ－ジイソヘキシルアミン、Ｎ，Ｎ－ジ（２－エチルヘキシル）アミン等）、直鎖状アルキル基を有する第三級アミン（トリブチルアミン、トリヘキシルアミン等）、分岐鎖状アルキル基を有する第三級アミン（トリイソヘキシルアミン、トリ（２－エチルヘキシル）アミン等）等であってもよい。 The above-mentioned monoamine (1) also includes, for example, primary amines having a cycloalkyl group (such as cyclohexylamine), primary amines having an alkenyl group (such as oleylamine), and secondary amines having a linear alkyl group. Amines (N,N-dipropylamine, N,N-dibutylamine, N,N-dipentylamine, N,N-dihexylamine, N,N-dipeptylamine, N,N-dioctylamine, N,N-dinonylamine, N,N-didecylamine, N,N-diundecylamine, N,N-didodecylamine, N-propyl-N-butylamine, etc.), secondary amines having branched alkyl groups (N,N-diiso hexylamine, N,N-di(2-ethylhexyl)amine, etc.), tertiary amines having a linear alkyl group (tributylamine, trihexylamine, etc.), tertiary amines having a branched alkyl group ( triisohexylamine, tri(2-ethylhexyl)amine, etc.).
　上記モノアミン（２）としては、高い配位能を有する点から、総炭素数２～５（より好ましくは３～５、更に好ましくは４～５）の直鎖状又は分岐鎖状アルキル基を有するアミン化合物が好ましい。 The monoamine (2) has a linear or branched alkyl group having a total carbon number of 2 to 5 (more preferably 3 to 5, still more preferably 4 to 5) from the viewpoint of having high coordinating ability. Amine compounds are preferred.
　上記モノアミン（２）の具体例としては、例えば、直鎖状又は分岐鎖状アルキル基を有する第一級アミン（エチルアミン、ｎ－プロピルアミン、イソプロピルアミン、ｎ－ブチルアミン、イソブチルアミン、ｓｅｃ－ブチルアミン、ｔｅｒｔ－ブチルアミン、ペンチルアミン、イソペンチルアミン、ｔｅｒｔ－ペンチルアミン等）、直鎖状又は分岐鎖状アルキル基を有する第二級アミン（Ｎ，Ｎ－ジメチルアミン、Ｎ，Ｎ－ジエチルアミン、Ｎ－メチル－Ｎ－プロピルアミン、Ｎ－エチル－Ｎ－プロピルアミン等）等が挙げられる。 Specific examples of the monoamine (2) include primary amines having a linear or branched alkyl group (ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, sec-butylamine, tert-butylamine, pentylamine, isopentylamine, tert-pentylamine, etc.), secondary amines having linear or branched alkyl groups (N,N-dimethylamine, N,N-diethylamine, N-methyl -N-propylamine, N-ethyl-N-propylamine, etc.).
　上記ジアミン（３）としては、２つのアミノ基の配位能が異なるため配位が複雑になりにくい点から、アミノ基とジ置換アミノ基を有するジアミンが好ましく、例えば、Ｎ，Ｎ－ジメチルエチレンジアミン、Ｎ，Ｎ－ジエチルエチレンジアミン、Ｎ，Ｎ－ジメチル－１，３－プロパンジアミン、Ｎ，Ｎ－ジエチル－１，３－プロパンジアミン、Ｎ，Ｎ－ジメチル－１，４－ブタンジアミン、Ｎ，Ｎ－ジエチル－１，４－ブタンジアミン、Ｎ，Ｎ－ジメチル－１，６－ヘキサンジアミン等が挙げられる。 As the diamine (3), a diamine having an amino group and a disubstituted amino group is preferable because the two amino groups have different coordinating abilities and the coordination is unlikely to be complicated. For example, N,N-dimethylethylenediamine. , N,N-diethylethylenediamine, N,N-dimethyl-1,3-propanediamine, N,N-diethyl-1,3-propanediamine, N,N-dimethyl-1,4-butanediamine, N,N -diethyl-1,4-butanediamine, N,N-dimethyl-1,6-hexanediamine, and the like.
　上記ジアミン（３）は、アミノ基を２つ有するジアミン（エチレンジアミン、１，３－プロパンジアミン、２，２－ジメチル－１，３－プロパンジアミン、１，４－ブタンジアミン、１，５－ペンタンジアミン、１，６－ヘキサンジアミン、１，７－ヘプタンジアミン、１，８－オクタンジアミン、１，５－ジアミノ－２－メチルペンタン等）、モノ置換アミノ基を２つ有するジアミン（Ｎ，Ｎ’－ジメチルエチレンジアミン、Ｎ，Ｎ’－ジエチルエチレンジアミン、Ｎ，Ｎ’－ジメチル－１，３－プロパンジアミン、Ｎ，Ｎ’－ジエチル－１，３－プロパンジアミン、Ｎ，Ｎ’－ジメチル－１，４－ブタンジアミン、Ｎ，Ｎ’－ジエチル－１，４－ブタンジアミン、Ｎ，Ｎ’－ジメチル－１，６－ヘキサンジアミン等）であってもよい。 The diamine (3) is a diamine having two amino groups (ethylenediamine, 1,3-propanediamine, 2,2-dimethyl-1,3-propanediamine, 1,4-butanediamine, 1,5-pentanediamine , 1,6-hexanediamine, 1,7-heptanediamine, 1,8-octanediamine, 1,5-diamino-2-methylpentane, etc.), diamines having two monosubstituted amino groups (N,N'- Dimethylethylenediamine, N,N'-diethylethylenediamine, N,N'-dimethyl-1,3-propanediamine, N,N'-diethyl-1,3-propanediamine, N,N'-dimethyl-1,4- butanediamine, N,N'-diethyl-1,4-butanediamine, N,N'-dimethyl-1,6-hexanediamine, etc.).
　上記モノアミン（１）、上記モノアミン（２）及び上記ジアミン（３）は、１種のみを用いてもよく、２種以上を用いてもよい。 Only one kind of the monoamine (1), the monoamine (2) and the diamine (3) may be used, or two or more kinds thereof may be used.
　上記アミンは、上記モノアミン（１）、上記モノアミン（２）及び上記ジアミン（３）以外に、他のアミン化合物を含有していてもよいが、上記アミン中の、他のアミン化合物の含有量は、上記モノアミン（１）、上記モノアミン（２）、上記ジアミン（３）及び上記他のアミン化合物の合計１００重量％に対して、４０．０重量％以下が好ましく、より好ましくは２０．０重量％以下、更に好ましくは１０．０重量％以下、特に好ましくは０重量％である。 The amine may contain other amine compounds in addition to the monoamine (1), the monoamine (2) and the diamine (3), but the content of the other amine compounds in the amine is , the monoamine (1), the monoamine (2), the diamine (3), and the other amine compound are preferably 40.0% by weight or less, more preferably 20.0% by weight, based on the total 100% by weight. Below, more preferably 10.0% by weight or less, particularly preferably 0% by weight.
　上記表面修飾金属ナノ粒子は、例えば、金属化合物と、上記有機保護剤とを混合して錯体を生成させ、生成した錯体を熱分解させることにより製造することができる。 The surface-modified metal nanoparticles can be produced, for example, by mixing the metal compound and the organic protective agent to form a complex, and thermally decomposing the resulting complex.
　上記金属化合物としては、例えば、金属カルボン酸塩（金属ギ酸塩、金属酢酸塩、金属シュウ酸塩、金属マロン酸塩、金属安息香酸塩、金属フタル酸塩等）、金属ハロゲン化物（金属フッ化物、金属塩化物、金属臭化物、金属ヨウ化物等）、金属無機酸塩（金属硫酸塩、金属硝酸塩、金属炭酸塩等）を用いることができる。中でも、分解により容易に金属を生成し且つ金属以外の不純物を生じにくいという点から、金属シュウ酸塩が好ましい。 Examples of the metal compounds include metal carboxylates (metal formates, metal acetates, metal oxalates, metal malonates, metal benzoates, metal phthalates, etc.), metal halides (metal fluorides , metal chlorides, metal bromides, metal iodides, etc.), metal inorganic acid salts (metal sulfates, metal nitrates, metal carbonates, etc.) can be used. Among them, metal oxalates are preferable because they easily generate metals by decomposition and are less likely to produce impurities other than metals.
　上記有機保護剤（好ましくは上記アミン）の使用量は、上記表面修飾金属ナノ粒子に十分な分散性を付与できる点から、上記金属化合物の金属原子１モルに対して、１～５０モルが好ましく、より好ましくは１０～４０モル、更に好ましくは１５～３５モルである。 The amount of the organic protective agent (preferably the amine) used is preferably 1 to 50 mol with respect to 1 mol of the metal atom of the metal compound, in terms of imparting sufficient dispersibility to the surface-modified metal nanoparticles. , more preferably 10 to 40 mol, still more preferably 15 to 35 mol.
　上記錯体を生成するための、上記金属化合物と上記有機保護剤との反応は、反応溶剤の存在下で行ってもよいし、反応溶剤の不存在下で行ってもよい。上記反応溶剤としては、例えば、炭素数３以上のアルコール系溶剤（好ましくは脂肪族アルコール）を用いることができる。 The reaction between the metal compound and the organic protective agent for forming the complex may be carried out in the presence of a reaction solvent or in the absence of a reaction solvent. As the reaction solvent, for example, an alcohol solvent (preferably an aliphatic alcohol) having 3 or more carbon atoms can be used.
　上記反応溶剤の使用量は、上記金属化合物１００重量部に対して、１２０～１０００重量部が好ましく、より好ましくは１３０～８００重量部、更に好ましくは１５０～５００重量部である。 The amount of the reaction solvent used is preferably 120 to 1000 parts by weight, more preferably 130 to 800 parts by weight, still more preferably 150 to 500 parts by weight, based on 100 parts by weight of the metal compound.
　上記錯体を生成する反応は、例えば、反応温度５～４０℃、反応時間３０分～３時間で行うことができる。 The reaction to generate the above complex can be carried out, for example, at a reaction temperature of 5 to 40°C and a reaction time of 30 minutes to 3 hours.
　上記熱分解は、上記反応溶剤と同様の反応溶剤の存在下で行ってもよい。熱分解温度は、例えば、８０～１２０℃が好ましく、より好ましくは１００～１１０℃であり、熱分解時間は、例えば、１０分～５時間である。また、上記錯体の熱分解は、空気雰囲気下や、不活性ガス（窒素、アルゴン等）雰囲気下で行うことができる。 The above thermal decomposition may be carried out in the presence of a reaction solvent similar to the above reaction solvent. The thermal decomposition temperature is, for example, preferably 80 to 120° C., more preferably 100 to 110° C., and the thermal decomposition time is, for example, 10 minutes to 5 hours. Moreover, the thermal decomposition of the complex can be carried out in an air atmosphere or an inert gas (nitrogen, argon, etc.) atmosphere.
　上記熱分解により得られた上記表面修飾金属ナノ粒子は、遠心分離やデカンテーションにより洗浄してもよい。 The surface-modified metal nanoparticles obtained by the thermal decomposition may be washed by centrifugation or decantation.
　上記表面修飾金属ナノ粒子中の上記有機保護剤の含有量は、上記表面修飾金属ナノ粒子１００重量％に対して、０．５～１０．０重量％が好ましく、より好ましくは１．０～７．０重量％、更に好ましくは１．５～５．０重量％である。上記有機保護剤の含有量が上記範囲内であると、表面修飾金属ナノ粒子が均一に分散しやすくなる The content of the organic protective agent in the surface-modified metal nanoparticles is preferably 0.5 to 10.0% by weight, more preferably 1.0 to 7%, based on 100% by weight of the surface-modified metal nanoparticles. 0% by weight, more preferably 1.5 to 5.0% by weight. When the content of the organic protective agent is within the above range, the surface-modified metal nanoparticles are easily dispersed uniformly.
＜フッ素系溶剤＞
　本開示の金属ナノ粒子含有分散液組成物は、分散媒としてフッ素系溶剤を含有する。上記フッ素系溶剤は、特に限定されないが、例えば、含フッ素芳香族炭化水素系溶剤、含フッ素炭化水素系溶剤、含フッ素エーテル系溶剤等が挙げられる。 <Fluorinated solvent>
The metal nanoparticle-containing dispersion composition of the present disclosure contains a fluorine-based solvent as a dispersion medium. The fluorinated solvent is not particularly limited, but examples thereof include fluorinated aromatic hydrocarbon solvents, fluorinated hydrocarbon solvents, and fluorinated ether solvents.
　上記含フッ素芳香族炭化水素系溶剤としては、例えば、１、３－ビス（トリフルオロメチル）ベンゼン、トリフルオロトルエン、オクタフルオロトルエン、ヘキサフルオロベンゼン等が挙げられる。 Examples of the fluorine-containing aromatic hydrocarbon solvent include 1,3-bis(trifluoromethyl)benzene, trifluorotoluene, octafluorotoluene, hexafluorobenzene and the like.
　上記含フッ素炭化水素系溶剤としては、例えば、パーフルオロペンタン、パーフルオロヘキサン、パーフルオロヘプタン、パーフルオロオクタン、パーフルオロノナン、パーフルオロデカン、パーフルオロメチルシクロヘキサン、オクタフルオロシクロペンテン、パーフルオロデカリン、パーフルオロ（１，３－ジメチルシクロヘキサン）、１，１，２，２，３，３，４－ヘプタフルオロシクロペンタン、１，１，１，２，３，４，４，５，５，５－デカフルオロペンタン、１，１，１，２，２，３，３，４，４，５，５，６，６－トリデカフルオロオクタン等が挙げられる。 Examples of the fluorine-containing hydrocarbon solvent include perfluoropentane, perfluorohexane, perfluoroheptane, perfluorooctane, perfluorononane, perfluorodecane, perfluoromethylcyclohexane, octafluorocyclopentene, perfluorodecalin, perfluorodecane, Fluoro(1,3-dimethylcyclohexane), 1,1,2,2,3,3,4-heptafluorocyclopentane, 1,1,1,2,3,4,4,5,5,5-deca fluoropentane, 1,1,1,2,2,3,3,4,4,5,5,6,6-tridecafluorooctane and the like.
　上記含フッ素エーテル系溶剤としては、例えば、ヘキサフルオロイソプロピルメチルエーテル、パーフルオロ（２－ブチルテトラヒドロフラン）、パーフルオロポリエーテル、メチルノナフルオロブチルエーテル、メチルノナフルオロイソブチルエーテル、エチルノナフルオロブチルエーテル、エチルノナフルオロイソブチルエーテル、１，１，１，２，３，４，４，５，５，５－デカフルオロ－３－メトキシ－２－（トリフルオロメチル）ペンタン、１，１，１，２，２，３，４，４，５，５，６，６，６－トリデカフルオロ－３－メトキシペンタン等）が挙げられる。 Examples of the fluorine-containing ether solvent include hexafluoroisopropyl methyl ether, perfluoro(2-butyltetrahydrofuran), perfluoropolyether, methyl nonafluorobutyl ether, methyl nonafluoroisobutyl ether, ethyl nonafluorobutyl ether, ethyl nonafluoro isobutyl ether, 1,1,1,2,3,4,4,5,5,5-decafluoro-3-methoxy-2-(trifluoromethyl)pentane, 1,1,1,2,2,3 , 4,4,5,5,6,6,6-tridecafluoro-3-methoxypentane, etc.).
　上記フッ素系溶剤は、１種のみを用いてもよく、２種以上を用いてもよい。 Only one type of the fluorine-based solvent may be used, or two or more types may be used.
　本開示の金属ナノ粒子含有分散液組成物は、上記フッ素系溶剤に加えて、効果を損なわない範囲で他の種類の溶剤を含んでいてもよい。 In addition to the fluorine-based solvent, the metal nanoparticle-containing dispersion composition of the present disclosure may contain other types of solvents within a range that does not impair the effect.
＜フッ素系分散剤＞
　本開示に係るフッ素系分散剤は、非反応性の含フッ素有機基と反応性基とを一分子内に有する含フッ素化合物であって、反応性基によって金属ナノ粒子の金属表面に吸着又は結合し、フッ素有機基により上記フッ素系溶剤と親和することによって、上記表面修飾金属ナノ粒子を上記フッ素系溶剤中において均一に分散させる。上記フッ素系分散剤は、構造中にフッ素を有する点で、上記有機保護剤とは異なる。 <Fluorine dispersant>
The fluorine-based dispersant according to the present disclosure is a fluorine-containing compound having a non-reactive fluorine-containing organic group and a reactive group in one molecule, and is adsorbed or bonded to the metal surface of the metal nanoparticles by the reactive group. Then, the surface-modified metal nanoparticles are uniformly dispersed in the fluorine-based solvent by having an affinity with the fluorine-based solvent due to the fluorine organic group. The fluorine-based dispersant differs from the organic protective agent in that it has fluorine in its structure.
　上記フッ素系分散剤が有する含フッ素有機基としては、例えば、フルオロアルキル基、フルオロアリール基等を含む基が挙げられる。上記フルオロアルキル基は、直鎖又は分岐鎖状のアルキル基について、水素原子の一部又は全部がフッ素原子に置き換わったものであり、上記フルオロアリール基とは、アリール基について、水素原子の一部又は全部がフッ素原子に置き換わったものである。 Examples of the fluorine-containing organic group possessed by the fluorine-based dispersant include groups containing a fluoroalkyl group, a fluoroaryl group, and the like. The fluoroalkyl group is a linear or branched alkyl group in which some or all of the hydrogen atoms are replaced with fluorine atoms, and the fluoroaryl group is an aryl group in which part of the hydrogen atoms are Alternatively, all of them are substituted with fluorine atoms.
　上記含フッ素有機基は、フルオロアルキルオキシ基又はフルオロアリールオキシ基と、１又は２以上のアルキレンオキシ基とが酸素原子を介して連なった基であってもよい。上記フルオロアルキルオキシ基は、直鎖又は分岐鎖状のアルキルオキシ基について、水素原子の一部又は全部がフッ素原子に置き換わったものであり、上記フルオロアリールオキシ基とは、アリールオキシ基について、水素原子の一部又は全部がフッ素原子に置き換わったものであり、上記アルキレンオキシ基とは、直鎖又は分岐鎖状のアルキレンオキシ基について、水素原子の一部又は全部がフッ素原子に置き換わったものである。 The fluorine-containing organic group may be a group in which a fluoroalkyloxy group or a fluoroaryloxy group and one or more alkyleneoxy groups are connected via an oxygen atom. The fluoroalkyloxy group is a linear or branched alkyloxy group in which some or all of the hydrogen atoms are replaced with fluorine atoms. Some or all of the atoms are replaced with fluorine atoms, and the above alkyleneoxy group is a linear or branched alkyleneoxy group in which some or all of the hydrogen atoms are replaced with fluorine atoms. be.
　上記含フッ素化合物が有する反応性基としては、例えば、カルボキシル基、アミノ基、チオール基、ヒドロキシル基、スルホ基、ホスホノ基、エステル基、アミド基、加水分解性シリル基等が挙げられ、中でも、金属ナノ粒子の安定的な分散性が得られやすい点から、加水分解性シリル基が好ましい。 Examples of reactive groups possessed by the fluorine-containing compound include carboxyl groups, amino groups, thiol groups, hydroxyl groups, sulfo groups, phosphono groups, ester groups, amide groups, hydrolyzable silyl groups, and the like. A hydrolyzable silyl group is preferred because it facilitates obtaining stable dispersibility of the metal nanoparticles.
　上記カルボキシル基を有する含フッ素化合物の具体例としては、例えば、２，３，４，５，６－ペンタフルオロ安息香酸、２，３，４，６－テトラフルオロ安息香酸、２，４，５－トリフルオロ安息香酸、２，３，４－トリフルオロ安息香酸、２－エチル－テトラフルオロ安息香酸、２－イソプロピル－テトラフルオロ安息香酸、３－シクロプロピル－２，４，５－トリフルオロ安息香酸、２－ブチル－テトラフルオロ安息香酸、ウンデカフルオロヘキサン酸、ノナデカフルオロデカン酸等が挙げられる。 Specific examples of the fluorine-containing compound having a carboxyl group include 2,3,4,5,6-pentafluorobenzoic acid, 2,3,4,6-tetrafluorobenzoic acid, 2,4,5- trifluorobenzoic acid, 2,3,4-trifluorobenzoic acid, 2-ethyl-tetrafluorobenzoic acid, 2-isopropyl-tetrafluorobenzoic acid, 3-cyclopropyl-2,4,5-trifluorobenzoic acid, 2-butyl-tetrafluorobenzoic acid, undecafluorohexanoic acid, nonadecafluorodecanoic acid and the like.
　上記アミノ基を有する含フッ素化合物の具体例としては、例えば、２，３，４，５，６－ペンタフルオロアニリン、２，３，４，５－テトラフルオロアニリン、２，４，５－トリフルオロフェニルアミン、４，５－ジフルオロ－２－アミノベンゾトリフルオリド、２－アミノ－５，６－ジフルオロ－ベンゾトリフルオリド、（３，４，５－トリフルオロフェニル）－（７－メトキシメチル－［１，４］－ジオキサノ［２，３－ｇ］キナゾリン－４－イル）－アミン、４－フルオロ－２－（トリフルオロメチル）－アニリン、３，４－ジフルオロアニリン、２－（ジフルオロメチル）－４－フルオロアニリン、２，２，３，３，４，４，５，５，６，６，７，７，８，８，８－ペンタデカフルオロオクタン－１－アミン等が挙げられる。 Specific examples of the fluorine-containing compound having an amino group include 2,3,4,5,6-pentafluoroaniline, 2,3,4,5-tetrafluoroaniline, 2,4,5-trifluoro Phenylamine, 4,5-difluoro-2-aminobenzotrifluoride, 2-amino-5,6-difluoro-benzotrifluoride, (3,4,5-trifluorophenyl)-(7-methoxymethyl-[1 ,4]-dioxano[2,3-g]quinazolin-4-yl)-amine, 4-fluoro-2-(trifluoromethyl)-aniline, 3,4-difluoroaniline, 2-(difluoromethyl)-4 -fluoroaniline, 2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-pentadecafluorooctan-1-amine and the like.
　上記チオール基を有する含フッ素化合物の具体例としては、例えば、４－トリフルオロメチルベンゼンチオール、３－トリフルオロメチルベンゼンチオール、ペンタフルオロベンゼンチオール、２，３，５，６－テトラフルオロベンゼンチオール、２，３，５，６－テトラフルオロ－４－（トリフルオロメチル）ベンゼンチオール、２，３，５，６－テトラフルオロ－４－メルカプト安息香酸メチルエステル、３，５－ビストリフルオロメチルベンゼンチオール、４－フルオロベンゼンチオール及び１１－（２，３，４，５，６－ペンタフルオロベンジルオキシ）－１－ウンデカンチオール（下記化学式）、１Ｈ，１Ｈ，２Ｈ，２Ｈ－パーフルオロデカンチオール、１Ｈ，１Ｈ，２Ｈ，２Ｈ－パーフルオロオクタンチオール等が挙げられる。 Specific examples of the fluorine-containing compound having a thiol group include 4-trifluoromethylbenzenethiol, 3-trifluoromethylbenzenethiol, pentafluorobenzenethiol, 2,3,5,6-tetrafluorobenzenethiol, 2,3,5,6-tetrafluoro-4-(trifluoromethyl)benzenethiol, 2,3,5,6-tetrafluoro-4-mercaptobenzoic acid methyl ester, 3,5-bistrifluoromethylbenzenethiol, 4-fluorobenzenethiol and 11-(2,3,4,5,6-pentafluorobenzyloxy)-1-undecanethiol (chemical formula below), 1H,1H,2H,2H-perfluorodecanethiol, 1H,1H , 2H,2H-perfluorooctanethiol and the like.
（フッ素系シラン化合物）
　本開示に係るフッ素系シラン化合物は、上記加水分解性シリル基を有する含フッ素化合物であって、例えば、下記式（１）で表される。
Figure JPOXMLDOC01-appb-C000001
 (Fluorine-based silane compound)
The fluorine-containing silane compound according to the present disclosure is a fluorine-containing compound having the hydrolyzable silyl group, and is represented by the following formula (1), for example.
Figure JPOXMLDOC01-appb-C000001
　式（１）中、Ｒは、フルオロアルキル基、又は、フルオロアルキルオキシ基及びフルオロアルキレンオキシ基を有する含フッ素有機基を示し、Ｘは、同一又は異なって、水素原子、ハロゲン原子、炭素数１～４のアルコキシ基、炭素数６～１０のアリールオキシ基、又は、炭素数１～４のアシルオキシ基を示し、Ｙは、同一又は異なって、炭素数１～１０のアルキル基、又は、炭素数３～１０のシクロアルキル基を示す。ｎは１～３の整数である。 In formula (1), R represents a fluoroalkyl group or a fluorine-containing organic group having a fluoroalkyloxy group and a fluoroalkyleneoxy group; -4 alkoxy group, aryloxy group having 6 to 10 carbon atoms, or acyloxy group having 1 to 4 carbon atoms, and Y is the same or different, an alkyl group having 1 to 10 carbon atoms, or an alkyl group having 1 to 10 carbon atoms It represents 3-10 cycloalkyl groups. n is an integer of 1-3.
　上記Ｒ中の炭素数は、好ましくは５～３００であり、より好ましくは１０～２００、更に好ましくは１５～１５０である。 The number of carbon atoms in R is preferably 5 to 300, more preferably 10 to 200, still more preferably 15 to 150.
　上記ｎは、安定的な分散性が得られやすい点から、２又は３であることが好ましく、より好ましくは３である。 The above n is preferably 2 or 3, more preferably 3, from the viewpoint of easily obtaining stable dispersibility.
　上記Ｘに係るハロゲン原子は、フッ素原子、塩素原子、臭素原子、ヨウ素原子が挙げられる。 The halogen atom for X above includes a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
　上記Ｘに係るアルコキシ基としては、例えば、メトキシ基、エトキシ基、ｎ－プロポキシ基、イソプロポキシ基、ｎ－ブトキシ基、ｓｅｃ－ブトキシ基、イソブトキシ基及びｔｅｒｔ－ブトキシ基等が挙げられる。 Examples of the alkoxy group for X include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy and tert-butoxy groups.
　上記Ｘに係るアリールオキシ基としては、例えば、フェノキシ基等が挙げられる。 Examples of the aryloxy group for X include a phenoxy group.
　上記Ｘに係るアシルオキシ基としては、アセチルオキシ基、プロピニルオキシ基、ピバロイルオキシ等が挙げられる。 Examples of the acyloxy group for X include an acetyloxy group, a propynyloxy group, and a pivaloyloxy group.
　上記Ｘは、アルコキシ基であることが好ましく、メトキシ基、エトキシ基であることがより好ましい。 The above X is preferably an alkoxy group, more preferably a methoxy group or an ethoxy group.
　上記Ｙに係るアルキル基としては、例えば、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、ｓｅｃ－ブチル基、イソブチル基、ｔｅｒｔ－ブチル基等が挙げられ、上記Ｙに係るシクロアルキル基としては、例えば、シクロブチル基、シクロペンチル基、シクロヘキシル基、シクロヘプチル基等が挙げられる。 Examples of the alkyl group for Y include methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, isobutyl group, tert-butyl group and the like, and the cycloalkyl group for Y above. Examples include cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group and the like.
　上記フッ素系シラン化合物の具体例示としては、例えば、（ヘプタデカフルオロ－１,１,２,２－テトラヒドロデシル）－トリエトキシシラン、（ヘプタデカフルオロ－１,１,２,２－テトラヒドロデシル）－トリメトキシシラン、ノナフルオロヘキシルトリエトキシシラン、ノナフルオロヘキシルトリメトキシシラン、（トリデカフルオロ－１,１,２,２－テトラヒドロオクチル）－トリエトキシシラン、（トリデカフルオロ－１,１,２,２－テトラヒドロオクチル）－トリメトキシシラン、ペンタフルオロ－１,１,２,２－テトラヒドロペンチルトリエトキシシラン、ペンタフルオロ－１,１,２,２－テトラヒドロペンチルトリメトキシシラン、（３,３,３－トリフルオロプロピル）ジメチルエトキシシラン、（３,３,３－トリフルオロプロピル）ジメチルメトキシシラン、（３,３,３－トリフルオロプロピル）メチルジエトキシシラン、（３,３,３－トリフルオロプロピル）メチルジメトキシシラン、（３,３,３－トリフルオロプロピル）トリエトキシシラン、（３,３,３－トリフルオロプロピル）トリメトキシシラン、パーフルオロプロピルトリエトキシシラン、パーフルオロプロピルトリメトキシシラン、５,５,６,６,７,７,８,８,９,９,１０,１０，１０－トリデカフルオロ－２－（トリデカフルオロヘキシル）デシルトリエトキシシラン、５,５,６,６,７,７,８,８,９,９,１０,１０,１０－トリデカフルオロ－２－（トリデカフルオロヘキシル）デシルトリメトキシシラン、パーフルオロドデシル－１Ｈ,１Ｈ,２Ｈ,２Ｈ－トリエトキシシラン、パーフルオロドデシル－１Ｈ,１Ｈ,２Ｈ,２Ｈ－トリメトキシシラン、パーフルオロテトラデシル－１Ｈ,１Ｈ,２Ｈ,２Ｈ－トリエトキシシラン、パーフルオロテトラデシル－１Ｈ,１Ｈ,２Ｈ,２Ｈ－トリメトキシシラン、３－（パーフルオロシクロヘキシルオキシ）プロピルトリメトキシシラン等が挙げられる。 Specific examples of the fluorine-based silane compound include (heptadecafluoro-1,1,2,2-tetrahydrodecyl)-triethoxysilane and (heptadecafluoro-1,1,2,2-tetrahydrodecyl). -trimethoxysilane, nonafluorohexyltriethoxysilane, nonafluorohexyltrimethoxysilane, (tridecafluoro-1,1,2,2-tetrahydrooctyl)-triethoxysilane, (tridecafluoro-1,1,2 ,2-tetrahydrooctyl)-trimethoxysilane, pentafluoro-1,1,2,2-tetrahydropentyltriethoxysilane, pentafluoro-1,1,2,2-tetrahydropentyltrimethoxysilane, (3,3, 3-trifluoropropyl)dimethylethoxysilane, (3,3,3-trifluoropropyl)dimethylmethoxysilane, (3,3,3-trifluoropropyl)methyldiethoxysilane, (3,3,3-trifluoro propyl)methyldimethoxysilane, (3,3,3-trifluoropropyl)triethoxysilane, (3,3,3-trifluoropropyl)trimethoxysilane, perfluoropropyltriethoxysilane, perfluoropropyltrimethoxysilane, 5,5,6,6,7,7,8,8,9,9,10,10,10-tridecafluoro-2-(tridecafluorohexyl)decyltriethoxysilane, 5,5,6,6 ,7,7,8,8,9,9,10,10,10-tridecafluoro-2-(tridecafluorohexyl)decyltrimethoxysilane, perfluorododecyl-1H,1H,2H,2H-triethoxy Silane, perfluorododecyl-1H,1H,2H,2H-trimethoxysilane, perfluorotetradecyl-1H,1H,2H,2H-triethoxysilane, perfluorotetradecyl-1H,1H,2H,2H-trimethoxysilane silane, 3-(perfluorocyclohexyloxy)propyltrimethoxysilane, and the like.
　また、上記フッ素系シラン化合物の好ましい例として、例えば、商品名「オプツールＨＤ－１１００ＴＨ」（ダイキン工業（株）製）が挙げられる。 Also, a preferable example of the fluorine-based silane compound is the trade name "OPTOOL HD-1100TH" (manufactured by Daikin Industries, Ltd.).
　上記フッ素系分散剤は、１種のみを用いてもよく、２種以上を用いてもよい。 Only one type of the fluorine-based dispersant may be used, or two or more types may be used.
　本開示の金属ナノ粒子含有分散液組成物中の上記フッ素系分散剤の含有量は、本開示の金属ナノ粒子含有分散液組成物１００重量％に対して、０．００１重量％以上が好ましく、より好ましくは０．００１～１０．０重量％、更に好ましくは０．００５～７．０重量％、特に好ましくは０．０１０～５．０重量％、最も好ましくは０．０５～３．０重量％である。上記フッ素系分散剤の含有量が上記範囲内であると、均一な分散状態を維持しやすくなる。 The content of the fluorine-based dispersant in the metal nanoparticle-containing dispersion composition of the present disclosure is preferably 0.001% by weight or more with respect to 100% by weight of the metal nanoparticle-containing dispersion composition of the present disclosure, More preferably 0.001 to 10.0 wt%, still more preferably 0.005 to 7.0 wt%, particularly preferably 0.010 to 5.0 wt%, most preferably 0.05 to 3.0 wt% %. When the content of the fluorine-based dispersant is within the above range, it becomes easier to maintain a uniform dispersed state.
　本開示の金属ナノ粒子含有分散液組成物中の上記フッ素系分散剤の含有量は、また、本開示の金属ナノ粒子１００重量部に対して、０．１重量部以上が好ましく、より好ましくは０．１～１０００重量部、更に好ましくは０．５～５００重量部、特に好ましくは１．０～２００重量部である。 The content of the fluorine-based dispersant in the metal nanoparticle-containing dispersion composition of the present disclosure is preferably 0.1 parts by weight or more, more preferably 100 parts by weight of the metal nanoparticles of the present disclosure. 0.1 to 1000 parts by weight, more preferably 0.5 to 500 parts by weight, particularly preferably 1.0 to 200 parts by weight.
（金属ナノ粒子含有分散液組成物の製造）
　本開示の金属ナノ粒子含有分散液組成物は、上記金属ナノ粒子、上記フッ素系溶剤及び上記フッ素系分散剤を混合して製造することができる。上記混合には、例えば、自公転式撹拌脱泡装置、ホモジナイザー、プラネタリーミキサー、３本ロールミル、ビーズミル等の一般的に知られる混合用機器を使用することができる。各成分は、同時に混合してもよいし、逐次混合してもよい。 (Production of dispersion composition containing metal nanoparticles)
The metal nanoparticle-containing dispersion composition of the present disclosure can be produced by mixing the metal nanoparticles, the fluorine-based solvent, and the fluorine-based dispersant. For the above mixing, for example, generally known mixing equipment such as a revolution-type stirring and degassing device, a homogenizer, a planetary mixer, a three-roll mill, and a bead mill can be used. Each component may be mixed simultaneously or sequentially.
　本開示の金属ナノ粒子含有分散液組成物は、長期に亘って上記金属ナノ粒子の分散性を安定的に維持できるので、例えば、コーティング剤として、あるいは、コーティング剤の原料として好適に使用することができる。 Since the metal nanoparticle-containing dispersion composition of the present disclosure can stably maintain the dispersibility of the metal nanoparticles over a long period of time, it can be suitably used, for example, as a coating agent or as a raw material for a coating agent. can be done.
［コーティング剤］
　本開示のコーティング剤は、本開示の金属ナノ粒子含有分散液組成物を含有する。本開示のコーティング剤が含有する金属ナノ粒子含有分散液組成物は、上記フッ素系溶剤を含む溶剤によって希釈されたものであってよい。本開示のコーティング剤中の上記金属ナノ粒子の含有量は、例えば、本開示のコーティング剤１００重量％に対して、０．００１～１０．０重量％が好ましく、より好ましくは０．００２～８．０重量％、更に好ましくは０．００５～５．０重量％である。 [Coating agent]
The coating agent of the present disclosure contains the metal nanoparticle-containing dispersion composition of the present disclosure. The metal nanoparticle-containing dispersion composition contained in the coating agent of the present disclosure may be diluted with a solvent containing the fluorine-based solvent. The content of the metal nanoparticles in the coating agent of the present disclosure is, for example, preferably 0.001 to 10.0 wt%, more preferably 0.002 to 8, relative to 100 wt% of the coating agent of the present disclosure. 0% by weight, more preferably 0.005 to 5.0% by weight.
　本開示の金属ナノ粒子含有分散液組成物を希釈して本開示のコーティング剤とする場合には、上記含フッ素化合物を適宜追加してもよい。 When the metal nanoparticle-containing dispersion composition of the present disclosure is diluted to form the coating agent of the present disclosure, the fluorine-containing compound may be added as appropriate.
　本開示のコーティング剤は、また、フッ素系溶剤に可溶な塗膜形成成分を含有していてもよい。上記塗膜形成成分としては、例えば、非晶性又は結晶性の含フッ素ポリマー（ポリパーフルオロブテニルビニルエーテル、テトラフルオロエチレン／パーフルオロ（ブテニルビニルエーテル）共重合体、テトラフルオロエチレン／パーフルオロ（プロペニルビニルエーテル）共重合体、テトラフルオロエチレン／パーフルオロ－２，２－ジメチル－１，３－ジオキソール共重合体、テトラフルオロエチレン／ヘキサフルオロプロピレン共重合体、ヘキサフルオロプロピレン／フッ化ビニリデン共重合体、テトラフルオロエチレン／パーフルオロメチルビニルエーテル共重合体、テトラフルオロエチレン／パーフルオロプロピルビニルエーテル共重合体等）や、上記加水分解性シリル基を有する含フッ素化合物とは別の、非反応性の含フッ素有機基及び重合性官能基（（メタ）アクリル基等）を有する重合性化合物等が挙げられる。 The coating agent of the present disclosure may also contain a coating film-forming component that is soluble in fluorine-based solvents. Examples of the coating film-forming component include amorphous or crystalline fluorine-containing polymers (polyperfluorobutenyl vinyl ether, tetrafluoroethylene/perfluoro(butenyl vinyl ether) copolymer, tetrafluoroethylene/perfluoro ( propenyl vinyl ether) copolymer, tetrafluoroethylene/perfluoro-2,2-dimethyl-1,3-dioxole copolymer, tetrafluoroethylene/hexafluoropropylene copolymer, hexafluoropropylene/vinylidene fluoride copolymer , tetrafluoroethylene/perfluoromethyl vinyl ether copolymer, tetrafluoroethylene/perfluoropropyl vinyl ether copolymer, etc.) and non-reactive fluorine-containing compounds other than the above fluorine-containing compounds having hydrolyzable silyl groups. Examples thereof include polymerizable compounds having an organic group and a polymerizable functional group ((meth)acrylic group, etc.).
　本開示の金属ナノ粒子含有分散液組成物中の上記フッ素系分散剤及び上記塗膜形成成分の合計の含有量は、上記表面修飾金属ナノ粒子１００重量部に対して、０．１重量部以上が好ましく、より好ましくは０．１～２００重量部、更に好ましくは０．５～１５０重量部、特に好ましくは１．０～１００重量部である。 The total content of the fluorine-based dispersant and the coating film-forming component in the metal nanoparticle-containing dispersion composition of the present disclosure is 0.1 parts by weight or more with respect to 100 parts by weight of the surface-modified metal nanoparticles. is preferred, more preferably 0.1 to 200 parts by weight, still more preferably 0.5 to 150 parts by weight, particularly preferably 1.0 to 100 parts by weight.
　本開示のコーティング剤を基材（透明プラスチック、ガラス等）の表面に塗布し、乾燥、固化させることによって、上記基材表面にコーティング層を形成することができる。 A coating layer can be formed on the substrate surface by applying the coating agent of the present disclosure to the surface of a substrate (transparent plastic, glass, etc.), drying, and solidifying.
　上記基材と上記コーティング層とを有する物品としては、例えば、光記録媒体（光磁気ディスク、光ディスク等）、光学部品（レンズ、プリズム、ペリクル、偏光板、光学フィルター、ミラー、ランプカバー、ライトカバー等）、各種画面表示機器（テレビ、ＰＣ用モニタ、携帯電話、ゲーム機、デジタルカメラ、現金自動支払機、カーナビゲーション装置等）のタッチパネル、保護ガラス（ショーウインドー、ショーケース等）、乗り物（車両、列車、航空機、船舶等）の窓ガラス等が挙げられる。 Examples of articles having the base material and the coating layer include optical recording media (magneto-optical discs, optical discs, etc.), optical components (lenses, prisms, pellicles, polarizing plates, optical filters, mirrors, lamp covers, light covers, etc.), various screen display devices (televisions, PC monitors, mobile phones, game consoles, digital cameras, cash dispensers, car navigation devices, etc.), protective glass (show windows, showcases, etc.), vehicles (vehicles, window glass of trains, aircraft, ships, etc.).
　上記の各実施形態における各構成及びそれらの組み合わせ等は、一例であって、本開示の主旨から逸脱しない範囲内において、適宜、構成の付加、省略、置換、及びその他の変更が可能である。本開示は、実施形態によって限定されることはなく、特許請求の範囲によってのみ限定される。 Each configuration, combination thereof, etc. in each of the above embodiments is an example, and addition, omission, substitution, and other modifications of configuration are possible as appropriate within the scope of the present disclosure. This disclosure is not limited by the embodiments, but only by the claims.
　以下、実施例により本開示をより具体的に説明するが、本開示はこれらの実施例により限定されない。 The present disclosure will be described in more detail below with reference to examples, but the present disclosure is not limited by these examples.
（調製例１） (Preparation Example 1)
　硝酸銀（富士フィルム和光純薬工業（株）製）とシュウ酸二水和物（富士フィルム和光純薬工業（株）製）からシュウ酸銀（分子量：３０３．７８）を得た。１００ｍＬフラスコにこのシュウ酸銀３．０ｇ（９．９ｍｍｏｌ）を仕込み、これに、ｎ－ブタノール（４．５ｇを添加し、シュウ酸銀のｎ－ブタノールスラリーを調製した。このスラリーに、３０℃で、ｎ－ブチルアミン（分子量：７３．１４、東京化成工業（株）製）８．６７ｇ（１１８．５ｍｍｏｌ）、ｎ－ヘキシルアミン（分子量：１０１．１９、東京化成工業（株）製）６．００ｇ（５９．３ｍｍｏｌ）、ｎ－オクチルアミン（分子量：１２９．２５、東京化成工業（株）製）５．７４ｇ（４４．４ｍｍｏｌ）、ｎ－ドデシルアミン（分子量：１８５．３５、東京化成工業（株）製）２．７５ｇ（４．８ｍｍｏｌ）及びＮ，Ｎ－ジメチル－１，３－プロパンジアミン（分子量：１０２．１８、東京化成工業（株）製）６．０５ｇ（５９．３ｍｍｏｌ）のアミン混合液を滴下した。滴下後、３０℃で２時間撹拌して、シュウ酸銀とアミンの錯形成反応を進行させ、白色物質（シュウ酸銀－アミン錯体）を得た。 Silver oxalate (molecular weight: 303.78) was obtained from silver nitrate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) and oxalic acid dihydrate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.). A 100 mL flask was charged with 3.0 g (9.9 mmol) of this silver oxalate, and 4.5 g of n-butanol was added thereto to prepare an n-butanol slurry of silver oxalate. 8.67 g (118.5 mmol) of n-butylamine (molecular weight: 73.14, manufactured by Tokyo Chemical Industry Co., Ltd.), n-hexylamine (molecular weight: 101.19, manufactured by Tokyo Chemical Industry Co., Ltd.)6. 00 g (59.3 mmol), n-octylamine (molecular weight: 129.25, manufactured by Tokyo Chemical Industry Co., Ltd.) 5.74 g (44.4 mmol), n-dodecylamine (molecular weight: 185.35, Tokyo Chemical Industry ( Co., Ltd.) 2.75 g (4.8 mmol) and N,N-dimethyl-1,3-propanediamine (molecular weight: 102.18, Tokyo Kasei Kogyo Co., Ltd.) 6.05 g (59.3 mmol) of amine After the dropwise addition, the mixture was stirred at 30° C. for 2 hours to promote complex formation reaction between silver oxalate and amine to obtain a white substance (silver oxalate-amine complex).
　シュウ酸銀－アミン錯体の形成後に、反応液温度を３０℃から１００℃まで昇温し、その後、１００℃を保持した状態で１時間加熱して、シュウ酸銀－アミン錯体を熱分解させて、濃青色の表面修飾銀ナノ粒子がアミン混合液中に懸濁した懸濁液を得た。 After the silver oxalate-amine complex is formed, the temperature of the reaction solution is raised from 30° C. to 100° C., and then heated for 1 hour while maintaining the temperature at 100° C. to thermally decompose the silver oxalate-amine complex. , a suspension of dark blue surface-modified silver nanoparticles in the amine mixture was obtained.
　冷却後、得られた懸濁液にメタノール３０ｇを加えて撹拌し、その後、遠心分離により表面修飾銀ナノ粒子を沈降させ、上澄み液を除去し、再度、メタノール９ｇを加えて撹拌し、その後、遠心分離により表面修飾銀ナノ粒子を沈降させ、上澄み液を除去した。このようにして、湿潤状態の表面修飾銀ナノ粒子を得た。動的光散乱法にて、得られた表面修飾銀ナノ粒子１の平均一次粒子径を確認したところ、２５ｎｍであった。 After cooling, 30 g of methanol is added to the resulting suspension and stirred, then the surface-modified silver nanoparticles are sedimented by centrifugation, the supernatant is removed, 9 g of methanol is added again and stirred, and then The surface-modified silver nanoparticles were sedimented by centrifugation, and the supernatant was removed. Thus, surface-modified silver nanoparticles in a wet state were obtained. When the average primary particle size of the obtained surface-modified silver nanoparticles 1 was confirmed by a dynamic light scattering method, it was 25 nm.
　上記湿潤状態の表面修飾銀ナノ粒子に、ｎ－ブタノール／ｎ－オクタン混合溶剤（重量比＝７０／３０）を加えて混合し、表面修飾銀ナノ粒子の含有量が５０重量％である液状組成物を調製した。 A liquid composition in which a mixed solvent of n-butanol/n-octane (weight ratio = 70/30) is added to and mixed with the surface-modified silver nanoparticles in a wet state so that the content of the surface-modified silver nanoparticles is 50% by weight. prepared the product.
　実施例及び比較例に使用した表面修飾銀ナノ粒子、フッ素系溶剤、フッ素系分散剤及びフッ素を含有しない分散剤は、以下の通りである。 The surface-modified silver nanoparticles, fluorine-based solvents, fluorine-based dispersants, and fluorine-free dispersants used in Examples and Comparative Examples are as follows.
（表面修飾銀ナノ粒子）
・銀ナノ粒子原液：調整例１で得られた銀ナノ粒子を含む液状組成物 (Surface-modified silver nanoparticles)
- Silver nanoparticles stock solution: liquid composition containing silver nanoparticles obtained in Preparation Example 1
（フッ素系溶剤）
・ＨＤ-ＴＨ：フッ素系溶剤、商品名「オプツールＨＤ-ＴＨ」、ダイキン工業（株）製
・パーフルオロヘキサン：商品名「テトラデカフルオロヘキサン」、東京化成工業（株）製 (fluorinated solvent)
・HD-TH: Fluorinated solvent, trade name “Optool HD-TH”, manufactured by Daikin Industries, Ltd. ・Perfluorohexane: trade name “Tetradecafluorohexane”, manufactured by Tokyo Chemical Industry Co., Ltd.
（フッ素系分散剤含有フッ素系溶剤）
・ＨＤ-１１００ＴＨ：フッ素系溶剤にフッ素系シラン化合物を０．１ｗｔ％混合したもの（ダイキン工業（株）製） (Fluorine-based solvent containing fluorine-based dispersant)
・HD-1100TH: A mixture of 0.1 wt% of a fluorine-based silane compound in a fluorine-based solvent (manufactured by Daikin Industries, Ltd.)
（フッ素を含有しない分散剤）
・ＤｉｓｐｅｒＢＹＫ１０６：酸基を有する高分子化合物の塩、ビックケミー・ジャパン（株）製
・ＤｉｓｐｅｒＢＹＫ１８０：酸基を有する共重合体のアルキロールアンモニウム塩、ビックケミー・ジャパン（株）製 (Dispersant containing no fluorine)
・DisperBYK106: Salt of polymer compound having acid group, manufactured by BYK-Chemie Japan Co., Ltd. ・DisperBYK180: Alkylolammonium salt of copolymer having acid group, manufactured by BYK-Chemie Japan Co., Ltd.
（実施例１）
　下記表１に記載の含有量（重量％）となるように、銀ナノ粒子原液（０．１ｇ）、ＨＤ-１１００ＴＨ（４．９ｇ）をテフロン（登録商標）容器に秤量し撹拌混合して銀ナノ微粒子分散液の評価サンプルを調整した。評価サンプルをシリンジフィルター（ＤＩＳＭＩＣ－２５ＣＳ０４５ＡＮ）を用いてろ過を行ったところ、黄色透明の液体が得られた。 (Example 1)
Silver nanoparticle undiluted solution (0.1 g) and HD-1100TH (4.9 g) were weighed into a Teflon (registered trademark) container and stirred and mixed so that the content (% by weight) shown in Table 1 below was obtained. An evaluation sample of the nanoparticle dispersion was prepared. When the evaluation sample was filtered using a syringe filter (DISMIC-25CS045AN), a yellow transparent liquid was obtained.
（実施例２）
　下記表１に記載の含有量（重量％）となるように配合した以外は実施例１と同様に行って評価サンプルを調製した。評価サンプルをシリンジフィルターでろ過すると、実施例１と同様、黄色透明の液体が得られた。 (Example 2)
An evaluation sample was prepared in the same manner as in Example 1 except that the content (% by weight) shown in Table 1 below was blended. When the evaluation sample was filtered with a syringe filter, a yellow transparent liquid was obtained as in Example 1.
（実施例３）
下記表１に記載の含有量（重量％）となるように配合した以外は実施例１と同様に行って評価サンプルを調製した。評価サンプルをシリンジフィルターでろ過すると、黒色透明の液体が得られた。 (Example 3)
An evaluation sample was prepared in the same manner as in Example 1 except that the content (% by weight) shown in Table 1 below was blended. When the evaluation sample was filtered with a syringe filter, a black transparent liquid was obtained.
（実施例４）
ＨＤ－１１００ＴＨを１０倍濃縮した後に、下記表１に記載の含有量（重量％）となるように配合した以外は実施例１と同様に行って評価サンプルを調製した。評価サンプルをシリンジフィルターでろ過すると、実施例１と同様、黄色透明の液体が得られた。 (Example 4)
An evaluation sample was prepared in the same manner as in Example 1 except that after concentrating HD-1100TH 10 times, it was blended so that the content (% by weight) shown in Table 1 below was obtained. When the evaluation sample was filtered with a syringe filter, a yellow transparent liquid was obtained as in Example 1.
（比較例１～４）
　下記表１に記載の含有量（重量％）となるように、銀ナノ粒子原液及びフッ素系溶剤、又は、銀ナノ粒子原液、フッ素系溶剤及びフッ素を含有しない分散剤をテフロン（登録商標）容器に秤量し撹拌混合して評価サンプルを調整した。評価サンプルをシリンジフィルターでろ過すると、無色透明の液体が得られた。 (Comparative Examples 1 to 4)
A silver nanoparticle stock solution and a fluorine-based solvent, or a silver nanoparticle stock solution, a fluorine-based solvent and a fluorine-free dispersant are placed in a Teflon (registered trademark) container so that the content (% by weight) shown in Table 1 below is obtained. were weighed and mixed with stirring to prepare an evaluation sample. When the evaluation sample was filtered with a syringe filter, a colorless and transparent liquid was obtained.
（銀ナノ粒子の分散性）
　実施例１～４、比較例１～４の評価サンプルをろ過した後の色を観察することによって、表面修飾銀ナノ粒子のフッ素系溶剤に対する分散性を評価した。評価基準は以下の通りである。 (Dispersibility of silver nanoparticles)
The dispersibility of the surface-modified silver nanoparticles in fluorine-based solvents was evaluated by observing the color after filtering the evaluation samples of Examples 1-4 and Comparative Examples 1-4. Evaluation criteria are as follows.
（評価基準）
〇（良好）：黄色～黒色に呈色していた
×（不良）：無色透明であった (Evaluation criteria)
〇 (Good): Colored yellow to black × (Poor): Colorless and transparent
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　表１より、表面修飾銀ナノ粒子、フッ素系溶剤及び含フッ素化合物を含有する実施例１～４の銀ナノ微粒子分散液では、表面修飾銀ナノ粒子のフッ素系溶剤に対する分散性に優れることが分かった（〇）。これに対して、含フッ素化合物を含有しない比較例１、２、含フッ素化合物の代わりにフッ素を含有しない分散剤を含有する比較例１、２では、何れも、表面修飾銀ナノ粒子のフッ素系溶剤に対する分散性に劣ることが分かった（×）。 From Table 1, it can be seen that the silver nanoparticle dispersions of Examples 1 to 4 containing the surface-modified silver nanoparticles, the fluorine-based solvent, and the fluorine-containing compound are excellent in the dispersibility of the surface-modified silver nanoparticles in the fluorine-based solvent. (〇). On the other hand, in Comparative Examples 1 and 2 containing no fluorine-containing compound, and in Comparative Examples 1 and 2 containing a fluorine-free dispersant instead of the fluorine-containing compound, both of the fluorine-based surface-modified silver nanoparticles It was found to be poor in dispersibility in solvents (×).
　以下、本開示に係る発明のバリエーションを記載する。
［付記１］金属ナノ粒子の表面が保護剤で被覆された構成を有する表面修飾金属ナノ粒子、フッ素系溶剤及びフッ素系分散剤を含有する、金属ナノ粒子含有分散液組成物。
［付記２］前記保護剤が、カルボキシル基、ヒドロキシル基、アミノ基、スルホ基及びチオール基からなる群より選択される少なくとも１種の反応性基を有する化合物である、付記１に記載の金属ナノ粒子含有分散液組成物。
［付記３］前記保護剤が、炭素数４～１８のアミンである、付記１に記載の金属ナノ粒子含有分散液組成物。
［付記４］前記保護剤が、総炭素数２～５（好ましくは３～５、より好ましくは４～５）の直鎖状又は分岐鎖状アルキル基を有するモノアミンである、付記１に記載の金属ナノ粒子含有分散液組成物。
［付記５］前記保護剤が、ｎ－ブチルアミンである、付記１に記載の金属ナノ粒子含有分散液組成物。
［付記６］前記表面修飾金属ナノ粒子の形状が、球状及び不定形状からなる群より選択される少なくとも１種である、付記１～５の何れか１つに記載の金属ナノ粒子含有分散液組成物。
［付記７］前記表面修飾金属ナノ粒子の平均一次粒子径が、３００ｎｍ以下である、付記１～６の何れか１つに記載の金属ナノ粒子含有分散液組成物。
［付記８］前記表面修飾金属ナノ粒子の平均一次粒子径が、１．０ｎｍ以上３００ｎｍ以下（好ましくは１００ｎｍ以下、より好ましくは８０ｎｍ以下、更に好ましくは５０ｎｍ以下）である、付記１～６の何れか１つに記載の金属ナノ粒子含有分散液組成物。
［付記９］前記有機保護剤の含有量が、前記表面修飾金属ナノ粒子１００重量％に対して、０．５～１０．０重量％（好ましくは１．０～７．０重量％、より好ましくは１．５～５．０重量％）である、付記１～８の何れか１つに記載の金属ナノ粒子含有分散液組成物。
［付記１０］前記フッ素系溶剤が、含フッ素芳香族炭化水素系溶剤、含フッ素炭化水素系溶剤及び含フッ素エーテル系溶剤からなる群より選択される少なくとも１種である、付記１～９の何れか１つに記載の金属ナノ粒子含有分散液組成物。
［付記１１］前記フッ素系溶剤が、パーフルオロペンタン、パーフルオロヘキサン、パーフルオロヘプタン、パーフルオロオクタン、パーフルオロノナン、パーフルオロデカン、パーフルオロメチルシクロヘキサン、オクタフルオロシクロペンテン、パーフルオロデカリン、パーフルオロ（１，３－ジメチルシクロヘキサン）、１，１，２，２，３，３，４－ヘプタフルオロシクロペンタン、１，１，１，２，３，４，４，５，５，５－デカフルオロペンタン、及び、１，１，１，２，２，３，３，４，４，５，５，６，６－トリデカフルオロオクタンからなる群より選択される少なくとも１種である、付記１～９の何れか１つに記載の金属ナノ粒子含有分散液組成物。
［付記１２］前記フッ素系分散剤が、非反応性の含フッ素有機基と反応性基とを一分子内に有する含フッ素化合物であり、前記含フッ素有機基が、フルオロアルキル基及び／又はフルオロアリール基を含む基である、付記１～１１の何れか１つに記載の金属ナノ粒子含有分散液組成物。
［付記１３］前記反応性基が、カルボキシル基、アミノ基、チオール基、ヒドロキシル基、スルホ基、ホスホノ基、エステル基、アミド基及び加水分解性シリル基からなる群より選択される少なくとも１種である、付記１２に記載の金属ナノ粒子含有分散液組成物。
［付記１４］前記フッ素系分散剤が、フッ素系シラン化合物である、付記１～１１の何れか１つに記載の金属ナノ粒子含有分散液組成物。
［付記１５］前記フッ素系分散剤が、下記式（１）で表されるフッ素系シラン化合物である、付記１～１１の何れか１つに記載の金属ナノ粒子含有分散液組成物。
Figure JPOXMLDOC01-appb-C000003
 （式（１）中、Ｒは、フルオロアルキル基、又は、フルオロアルキルオキシ基及びフルオロアルキレンオキシ基を有する含フッ素有機基を示し、Ｘは、同一又は異なって、水素原子、ハロゲン原子、炭素数１～４のアルコキシ基、炭素数６～１０のアリールオキシ基、又は、炭素数１～４のアシルオキシ基を示し、Ｙは、同一又は異なって、炭素数１～１０のアルキル基、又は、炭素数３～１０のシクロアルキル基を示す。ｎは１～３の整数である）
［付記１６］前記フッ素系分散剤の含有量が、前記金属ナノ粒子含有分散液組成物１００重量％に対して、０．００１重量％以上（好ましくは０．００１～１０．０重量％、より好ましくは０．００５～７．０重量％、更に好ましくは０．０１０～５．０重量％、特に好ましくは０．０５～３．０重量％）である、付記１～１５の何れか１つに記載の金属ナノ粒子含有分散液組成物。
［付記１７］前記フッ素系分散剤の含有量が、前記金属ナノ粒子１００重量部に対して、０．１重量部以上（好ましく０．１～１０００重量部、より好ましくは０．５～５００重量部、更に好ましくは１．０～２００重量部である、付記１～１６の何れか１つに記載の金属ナノ粒子含有分散液組成物。
［付記１８］付記１～１７の何れか１つに記載の金属ナノ粒子含有分散液組成物を含有する、コーティング剤。
［付記１９］前記金属ナノ粒子の含有量が、前記コーティング剤１００重量％に対して、０．００１～１０．０重量％（好ましくは０．００２～８．０重量％、より好ましくは０．００５～５．０重量％）である、付記１８に記載のコーティング剤。
［付記２０］基材と、前記基材表面に付記１９に記載のコーティング剤から形成されるコーティング層とを有する物品。 Variations of the invention according to the present disclosure are described below.
[Appendix 1] A metal nanoparticle-containing dispersion liquid composition containing surface-modified metal nanoparticles having a structure in which the surfaces of the metal nanoparticles are coated with a protective agent, a fluorine-based solvent, and a fluorine-based dispersant.
[Appendix 2] The metal nanoparticles according to Appendix 1, wherein the protective agent is a compound having at least one reactive group selected from the group consisting of a carboxyl group, a hydroxyl group, an amino group, a sulfo group and a thiol group. A particle-containing dispersion composition.
[Appendix 3] The metal nanoparticle-containing dispersion composition according to Appendix 1, wherein the protective agent is an amine having 4 to 18 carbon atoms.
[Appendix 4] According to appendix 1, the protective agent is a monoamine having a linear or branched alkyl group with a total carbon number of 2 to 5 (preferably 3 to 5, more preferably 4 to 5). A dispersion composition containing metal nanoparticles.
[Appendix 5] The metal nanoparticle-containing dispersion composition according to Appendix 1, wherein the protective agent is n-butylamine.
[Appendix 6] The metal nanoparticle-containing dispersion composition according to any one of Appendices 1 to 5, wherein the shape of the surface-modified metal nanoparticles is at least one selected from the group consisting of spherical and irregular shapes. thing.
[Appendix 7] The metal nanoparticle-containing dispersion composition according to any one of Appendices 1 to 6, wherein the average primary particle size of the surface-modified metal nanoparticles is 300 nm or less.
[Appendix 8] Any of Appendices 1 to 6, wherein the average primary particle size of the surface-modified metal nanoparticles is 1.0 nm or more and 300 nm or less (preferably 100 nm or less, more preferably 80 nm or less, and still more preferably 50 nm or less). or the metal nanoparticle-containing dispersion composition according to any one of the above.
[Appendix 9] The content of the organic protective agent is 0.5 to 10.0 wt% (preferably 1.0 to 7.0 wt%, more preferably is 1.5 to 5.0% by weight), the metal nanoparticle-containing dispersion composition according to any one of appendices 1 to 8.
[Appendix 10] Any of Appendices 1 to 9, wherein the fluorine-based solvent is at least one selected from the group consisting of a fluorine-containing aromatic hydrocarbon solvent, a fluorine-containing hydrocarbon solvent, and a fluorine-containing ether solvent. or the metal nanoparticle-containing dispersion composition according to any one of the above.
[Appendix 11] The fluorine-based solvent is perfluoropentane, perfluorohexane, perfluoroheptane, perfluorooctane, perfluorononane, perfluorodecane, perfluoromethylcyclohexane, octafluorocyclopentene, perfluorodecalin, perfluoro ( 1,3-dimethylcyclohexane), 1,1,2,2,3,3,4-heptafluorocyclopentane, 1,1,1,2,3,4,4,5,5,5-decafluoropentane , and at least one selected from the group consisting of 1,1,1,2,2,3,3,4,4,5,5,6,6-tridecafluorooctane, Appendices 1 to 9 Metal nanoparticle-containing dispersion liquid composition according to any one of.
[Appendix 12] The fluorine-containing dispersant is a fluorine-containing compound having a non-reactive fluorine-containing organic group and a reactive group in one molecule, and the fluorine-containing organic group is a fluoroalkyl group and/or a fluoro The metal nanoparticle-containing dispersion composition according to any one of Appendices 1 to 11, which is a group containing an aryl group.
[Appendix 13] The reactive group is at least one selected from the group consisting of a carboxyl group, an amino group, a thiol group, a hydroxyl group, a sulfo group, a phosphono group, an ester group, an amide group and a hydrolyzable silyl group. 13. The metal nanoparticle-containing dispersion composition according to Appendix 12.
[Appendix 14] The metal nanoparticle-containing dispersion composition according to any one of Appendices 1 to 11, wherein the fluorine-based dispersant is a fluorine-based silane compound.
[Appendix 15] The metal nanoparticle-containing dispersion composition according to any one of Appendices 1 to 11, wherein the fluorine-based dispersant is a fluorine-based silane compound represented by the following formula (1).
Figure JPOXMLDOC01-appb-C000003
 (In formula (1), R represents a fluoroalkyl group, or a fluorine-containing organic group having a fluoroalkyloxy group and a fluoroalkyleneoxy group, and X is the same or different, a hydrogen atom, a halogen atom, a carbon number an alkoxy group having 1 to 4 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, or an acyloxy group having 1 to 4 carbon atoms, and Y is the same or different, an alkyl group having 1 to 10 carbon atoms, or carbon represents a cycloalkyl group of numbers 3 to 10. n is an integer of 1 to 3)
[Appendix 16] The content of the fluorine-based dispersant is 0.001% by weight or more (preferably 0.001 to 10.0% by weight, more than Preferably 0.005 to 7.0% by weight, more preferably 0.010 to 5.0% by weight, particularly preferably 0.05 to 3.0% by weight), any one of appendices 1 to 15 The metal nanoparticle-containing dispersion composition according to .
[Appendix 17] The content of the fluorine-based dispersant is 0.1 parts by weight or more (preferably 0.1 to 1000 parts by weight, more preferably 0.5 to 500 parts by weight with respect to 100 parts by weight of the metal nanoparticles Parts, more preferably 1.0 to 200 parts by weight, the metal nanoparticle-containing dispersion composition according to any one of Appendixes 1 to 16.
[Appendix 18] A coating agent containing the metal nanoparticle-containing dispersion composition according to any one of Appendices 1 to 17.
[Appendix 19] The content of the metal nanoparticles is 0.001 to 10.0 wt% (preferably 0.002 to 8.0 wt%, more preferably 0.002 to 8.0 wt%, more preferably 0.001 to 10.0 wt% with respect to 100 wt% of the coating agent). 005 to 5.0% by weight), the coating agent according to Appendix 18.
[Appendix 20] An article comprising a substrate and a coating layer formed from the coating agent according to Appendix 19 on the surface of the substrate.
　本開示の金属ナノ粒子含有分散液組成物では、金属ナノ粒子のフッ素系溶剤に対する分散性が向上するので、これを含有するコーティング剤を用いて、ガラス等の基材上に、金属ナノ粒子を均一に含むコーティング層を形成することが可能となる。従って、本開示は、産業上の利用可能性を有する。 In the metal nanoparticle-containing dispersion composition of the present disclosure, the dispersibility of the metal nanoparticles in fluorine-based solvents is improved. A uniform coating layer can be formed. Therefore, the present disclosure has industrial applicability.

Claims (6)

  1. 　金属ナノ粒子の表面が保護剤で被覆された構成を有する表面修飾金属ナノ粒子、フッ素系溶剤及びフッ素系分散剤を含有する、金属ナノ粒子含有分散液組成物。 A metal nanoparticle-containing dispersion liquid composition containing surface-modified metal nanoparticles having a structure in which the surfaces of the metal nanoparticles are coated with a protective agent, a fluorine-based solvent, and a fluorine-based dispersant.
  2. 　前記保護剤が、カルボキシル基、ヒドロキシル基、アミノ基、スルホ基及びチオール基からなる群より選択される少なくとも１種の反応性基を有する化合物である、請求項１に記載の金属ナノ粒子含有分散液組成物。 The metal nanoparticle-containing dispersion according to claim 1, wherein the protective agent is a compound having at least one reactive group selected from the group consisting of a carboxyl group, a hydroxyl group, an amino group, a sulfo group and a thiol group. liquid composition.
  3. 　前記表面修飾金属ナノ粒子の平均一次粒子径が、３００ｎｍ以下である、請求項１又は２に記載の金属ナノ粒子含有分散液組成物。 The metal nanoparticle-containing dispersion composition according to claim 1 or 2, wherein the surface-modified metal nanoparticles have an average primary particle size of 300 nm or less.
  4. 　前記フッ素系分散剤が、フッ素系シラン化合物である、請求項１～３の何れか１項に記載の金属ナノ粒子含有分散液組成物。 The dispersion composition containing metal nanoparticles according to any one of claims 1 to 3, wherein the fluorine-based dispersant is a fluorine-based silane compound.
  5. 　請求項１～４の何れか１項に記載の金属ナノ粒子含有分散液組成物を含有する、コーティング剤。 A coating agent containing the metal nanoparticle-containing dispersion composition according to any one of claims 1 to 4.
  6. 　基材と、前記基材表面に請求項５に記載のコーティング剤から形成されるコーティング層とを有する物品。 An article having a base material and a coating layer formed from the coating agent according to claim 5 on the surface of the base material.
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