JP4505825B2 - Method for sintering metal nanoparticles and method for forming wiring on a substrate using the sintering method - Google Patents

Description

  The present invention relates to a method for sintering metal nanoparticles and a method for forming wiring on a substrate using the sintering method.

The metal nanoparticles are particles composed of a limited number of metal atoms having a particle size of nanometer, that is, a size of 10 ⁻⁹ m. Such metal nanoparticles have a very large surface area per unit mass, and therefore the surface is very active. On the other hand, metal nanoparticles tend to aggregate naturally and tend to be coarse. If it becomes so coarse, the original properties of the metal nanoparticles are lost, and thus a coating that protects the surface of the metal nanoparticles is formed (for example, see Patent Documents 1 to 3). ). As the coating, a coating having a site that interacts with the surface of the metal nanoparticles at a number of points, for example, strongly coordinated to the surface of the metal nanoparticles is used.

  Such metal nanoparticles are conventionally used as a material for forming wiring. When forming the wiring, generally, a paste in which metal nanoparticles are dispersed in a dispersion solvent is used, a pattern is formed on the wiring substrate, and the metal nanoparticles in the paste are sintered to form the wiring.

  However, as described above, the metal nanoparticles have a coating on the outside of the particles in order to prevent aggregation. In order to sinter the metal nanoparticles in the paste, it is necessary to peel off the coating from the metal nanoparticles. For this purpose, heating at a high temperature, for example, 200 ° C. or higher is required (for example, see Non-Patent Document 1). When heating at such a high temperature is necessary, there is a drawback that only a substrate made of a material resistant to heating can be used as the wiring substrate.

On the other hand, metal nanoparticles that weaken the bond between the coating and the metal nanoparticles and enable the metal nanoparticles to be sintered at a low temperature have been reported (see, for example, Patent Document 4). However, such a paste containing coated metal nanoparticles having a weak bond between the coating and the metal nanoparticles lacks long-term stability and is easily altered by storage. When the wiring board is formed using the altered paste, there is a problem that a trade-off is likely to occur.
JP 2004-119686 A JP 2005-307335 A JP 2004-273205 A JP 2003-187640 A Katsuaki Kakinuma et al., “Curing characteristics of nano paste for fine printed circuits”, Proc. 3rd International IEEE Conference on Polymers and Adhesives in Microelectronics and Photonics, Polytronic 2003, Switzerland, 2003, p. 369-374.

  Therefore, an object of the present invention is to provide a method for sintering coated metal nanoparticles having excellent storage stability that can be carried out regardless of temperature.

  The present invention relates to a method for sintering metal nanoparticles, wherein the method includes a polar paste containing a polar solvent or a solubilizing agent in a metal nanoparticle paste containing coated metal nanoparticles and a dispersion solvent on a substrate. A step of applying a solvent solution and a step of drying the substrate.

  The present invention has the advantage that it can be implemented regardless of temperature. Therefore, there is an advantage that the material of the wiring board is not limited. The present invention also has the advantage that the coated metal nanoparticles having excellent storage stability can be sintered. Therefore, it is possible to use a commercially available coated metal nanoparticle paste having excellent storage stability.

  As described above, the present invention is a method for sintering metal nanoparticles, wherein the method includes dissolving a polar solvent or a solution in a metal nanoparticle paste including a coated metal nanoparticle and a dispersion solvent on a substrate. A step of applying a polar solvent solution containing an auxiliary agent and a step of drying the substrate.

  Moreover, this invention is a method of forming wiring on a board | substrate using the sintering method of the metal nanoparticle of this invention. The method includes a step of forming a pattern to be a wiring precursor on a substrate using a metal nanoparticle paste including coated metal nanoparticles and a dispersion solvent, and a polar solvent or a dissolution in the pattern on the substrate. A step of applying a polar solvent solution containing an auxiliary agent; and a step of drying the substrate to sinter the metal nanoparticles to form a wiring. Any of the step of forming a pattern to be the wiring precursor on the substrate and the step of applying a polar solvent solution containing the polar solvent or dissolution aid may be performed first.

  In the method for sintering the metal nanoparticles and the method for forming the wiring on the substrate, the metal nanoparticles are silver, copper, gold, platinum, rhodium, nickel, platinum-gold alloy, platinum-palladium alloy, gold- Silver alloy, silver-palladium alloy, palladium-gold alloy, platinum-gold alloy, rhodium-palladium alloy, silver-rhodium alloy, copper-palladium alloy, nickel-palladium alloy, iron-platinum alloy, iron-platinum-copper alloy, Particles formed from one or more metals selected from the group consisting of iron-platinum-tin alloys, iron-platinum-bismuth alloys and iron-platinum-lead alloys, or silver, copper, gold, platinum, rhodium, nickel, Platinum-gold alloy, platinum-palladium alloy, gold-silver alloy, silver-palladium alloy, palladium-gold alloy, platinum-gold alloy, rhodium-palladium alloy, silver-rhodium alloy, copper Two or more selected from the group consisting of palladium alloy, nickel-palladium alloy, iron-platinum alloy, iron-platinum-copper alloy, iron-platinum-tin alloy, iron-platinum-bismuth alloy and iron-platinum-lead alloy Particles having a core-shell structure formed from metal are preferred.

In the method for sintering the metal nanoparticles and the method for forming a wiring on the substrate, the metal nanoparticles may be coated with a heterocyclic ring and an alkyl-substituted heterocyclic ring, as well as -COOH, -SH, -SOH, -SO. ₂ H, —SO ₃ H, —NH ₂ , —NOH, —NO ₂ H, —OH, —SiOH, —Si (OH) ₂ , —Si (OH) ₃ , —PO ₂ H ₂ , —PO ₃ H ₂ , —PO ₄ H, —COO—, —CON—, —CONH—, —CONH ₂ , —S—, —SO—, —SO ₂ —, —NH—, —NO—, —O—, —SiO ₂ -, - PH -, - PH 2 -, - PO -, - POH -, - POH 2 -, - PO 2 -, - PO 2 H -, - PO 3 -, - PO 3 H -, - PO 4 - An alkane containing one or more selected from the group consisting of: -N (-)-, -Si (O-) ₂ and -Si (O-) ₃ ; It is preferably formed from one or more selected from the group consisting of alkenes, alkynes, aromatic hydrocarbons, alkyl-substituted aromatic hydrocarbons, heterocycles and alkyl-substituted heterocycles.

  In the method for sintering the metal nanoparticles and the method for forming a wiring on the substrate, the dispersion solvent is alkane, alkene, alkyne, alicyclic hydrocarbon, aromatic hydrocarbon, alkyl-substituted aromatic hydrocarbon. And one or more selected from the group consisting of terpene hydrocarbons containing one or more —OH.

In the method for sintering the metal nanoparticles and the method for forming a wiring on the substrate, the polar solvent in the polar solvent or the polar solvent solution containing the dissolution aid is a heterocycle, an alkyl-substituted heterocycle, water. , -COOH, -SH, -SOH, -SO 2 H, -SO 3 H, alkane substituted with one or more selected from the group consisting of -NH ₂ and -OH, alkenes, alkynes, aromatic hydrocarbons, It is preferably one or more polar solvents selected from the group consisting of alkyl-substituted aromatic hydrocarbons, heterocycles, alkyl-substituted heterocycles, and compounds represented by the following formula (X).
R ²¹ -Y-R ²² (X)
In the formula (X), R ²¹ and R ²² are each independently an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an alkyl-substituted aryl group, a heteroaryl group or an alkyl-substituted heteroaryl group. Yes,
Y is a group represented by —CONH—, —C (═O) —, or —SO—.

  In the method for sintering metal nanoparticles and the method for forming wiring on the substrate, the dissolution aid is preferably one or more selected from the group consisting of polyvinylpyrrolidone and polyvinyl alcohol.

  In the method for sintering the metal nanoparticles and the method for forming the wiring on the substrate, the step of applying the polar solvent or the polar solvent solution containing the dissolution aid is performed at a temperature in the range of −20 ° C. to 150 ° C. Are preferred.

  In the method for sintering metal nanoparticles and the method for forming wiring on the substrate, the substrate is selected from the group consisting of thermoplastic resin, thermosetting resin, glass, paper, metal, silicon, and ceramics. It is preferable to be formed from the above materials.

  Examples of various definitions, preferred examples, and specific examples used in the above and following descriptions of the present specification will be described below.

Alkane means an acyclic saturated hydrocarbon represented by the formula C _n H _{2n + 2} , and examples thereof include those having 1 to 100 carbon atoms. The alkane includes a chain shape and a branched shape. The alkane is preferably an alkane having 1 to 20 carbon atoms, such as methane, ethane, propane, butane, pentane, hexane, heptane, 2,2,2,4-trimethylpentane, octane, nonane, decane, undecane, dodecane. , Tridecane, tetradecane, pentadecane, hexadecane, heptadecane, octadecane, nonadecane, icosane, etc., more preferably alkanes having 5 to 15 carbon atoms, such as pentane, hexane, heptane, 2,2,2,4-trimethylpentane, octane. , Nonane, decane, undecane, dodecane, tridecane, tetradecane, pentadecane, etc., more preferably an alkane having 8 to 15 carbon atoms, such as 2,2,2,4-trimethylpentane, octane, nonane, decane, undecane, dodecane. The Decane, tetradecane, a pentadecane, etc., even more preferably 2,2,2,4- trimethylpentane, tetradecane.

—COOH, —SH, —SOH, —SO ₂ H, —SO ₃ H, —NH ₂ , —NOH, —NO ₂ H, —OH, —SiOH, —Si (OH) ₂ , —Si (OH) ₃ , —PO ₂ H ₂ , —PO ₃ H ₂ , —PO ₄ H, —COO—, —CON—, —CONH—, —CONH ₂ , —S—, —SO—, —SO ₂ —, —NH— , -NO -, - O -, - SiO -, - PH -, - PH 2 -, - PO -, - POH -, - POH 2 -, - PO 2 -, - PO 2 H -, - PO 3 - _{, -PO 3 H -, - PO} 4 -, - N (-) -, - Si (O-) as the alkane containing ₂ and -Si (O-) 1 or more selected from the group consisting of _3, the Means containing one or more of the above substituents in alkane, such as formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, isovaleric acid, pivalic acid, etc., hexa Acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, methanol, ethanol, isopropanol, 2-methyl-2-propanol, butanol, pentanol, hexanol, heptanol, Octanol, nonaol, decanol, undecanol, dodecanol, tridecanol, pentadecanol, hexadecanol, heptadecanol, octadecanol, nonadecanol, icosanol, methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine, heptylamine , Octylamine, nonylamine, decylamine, undecylamine, dodecylamine, tetradecylamine, pentadecylamine, hexadecylamine, hepta Silamine, octadecylamine, nonadecylamine, icosanylamine, methanethiol, ethanethiol, propanethiol, butanethiol, pentanethiol, hexanethiol, heptanethiol, octanethiol, nonanethiol, decanethiol, undecanethiol, dodecanethiol, tridecanethiol, tetradecane Examples include thiol, pentadecanethiol, hexadecanethiol, heptadecanethiol, octadecanethiol, nonadecanethiol, icosanethiol, and dimethyl ether. The _{-COOH, -SH, -SOH, -SO 2} H, -SO 3 H, -NH 2, -NOH, -NO 2 H, -OH, -SiOH, -Si (OH) 2, -Si (OH) ₃ , —PO ₂ H ₂ , —PO ₃ H ₂ , —PO ₄ H, —COO—, —CON—, —CONH—, —CONH ₂ , —S—, —SO—, —SO ₂ —, —NH -, - NO -, - O -, - SiO -, - PH -, - PH 2 -, - PO -, - POH -, - POH 2 -, - PO 2 -, - PO 2 H -, - PO 3 The alkane containing one or more selected from the group consisting of —, —PO ₃ H—, —PO ₄ —, —N (—) —, —Si (O—) ₂ and —Si (O—) ₃ Preferred are lauric acid, myristic acid, palmitic acid, stearic acid, dodecylamine, dodecanethiol and the like.

—COOH, —SH, —SOH, —SO ₂ H, —SO ₃ H, —NH ₂ , —NOH, —NO ₂ H, —OH, —SiOH, —Si (OH) ₂ , —Si (OH) ₃ , —PO ₂ H ₂ , —PO ₃ H _2, and —PO ₄ H are alkanes substituted with one or more selected from the group consisting of one or more hydrogen atoms of the alkanes substituted with one or more of the substituents For example, formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, isovaleric acid, pivalic acid, etc., hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, lauric acid, myristic Acid, palmitic acid, stearic acid, methanesulfonic acid, methanol, ethanol, isopropanol, 2-methyl-2-propanol, butanol, pentanol, hexanol, heptanol, octanol, Naol, decanol, undecanol, dodecanol, tridecanol, pentadecanol, hexadecanol, heptadecanol, octadecanol, nonadecanol, icosanol, methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine, heptylamine, octyl Amine, nonylamine, decylamine, undecylamine, dodecylamine, tetradecylamine, pentadecylamine, hexadecylamine, heptadecylamine, octadecylamine, nonadecylamine, icosanylamine, methanethiol, ethanethiol, propanethiol, butanethiol, pentanethiol , Hexanethiol, heptanethiol, octanethiol, nonanethiol, decanethiol, unde Examples include canthiol, dodecanethiol, tridecanethiol, tetradecanethiol, pentadecanethiol, hexadecanethiol, heptadecanethiol, octadecanethiol, nonadecanethiol, and icosanethiol. The substituted alkane is preferably lauric acid, myristic acid, palmitic acid, stearic acid, dodecylamine, dodecanethiol and the like.

The alkane substituted with one or more selected from the group consisting of —COOH, —SH, —SOH, —SO ₂ H, —SO ₃ H, —NH ₂ and —OH has one or more hydrogen atoms of the alkane. Meaning one or more substituted with the above substituents, for example, formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, isovaleric acid, pivalic acid, etc., hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, Decanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, methanesulfonic acid, methanol, ethanol, isopropanol, 2-methyl-2-propanol, butanol, pentanol, hexanol, heptanol, octanol, nonaol, decanol, undecanol, Dodecanol, tridecanol, pentadecanol, hexadecanol, heptadecane , Octadecanol, nonadecanol, icosanol, methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, undecylamine, dodecylamine, tetradecylamine, pentadecyl Amine, hexadecylamine, heptadecylamine, octadecylamine, nonadecylamine, icosanylamine, methanethiol, ethanethiol, propanethiol, butanethiol, pentanethiol, hexanethiol, heptanethiol, octanethiol, nonanethiol, decanethiol, undecanethiol, Dodecanethiol, tridecanethiol, tetradecanethiol, pentadecanethiol, hexadecanethiol , Heptadecanethiol, octadecanethiol, nonadecanethiol, icosanethiol and the like. The substituted alkane is preferably lauric acid, myristic acid, palmitic acid, stearic acid, dodecylamine, dodecanethiol and the like.

  The alkane substituted with —COOH means that one or more hydrogen atoms of the alkane are substituted with one or more —COOH, for example, 1-10 hydrogen atoms of an alkane having 1 to 50 carbon atoms are —COOH. And those substituted with 1-10. The alkane substituted with -COOH is preferably an alkane having 1 to 20 carbon atoms substituted with -COOH, such as formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, isovaleric acid, pivalic acid and the like. , Hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, etc., more preferably an alkane having 10 to 20 carbon atoms substituted with —COOH, such as decane Acid, lauric acid, myristic acid, palmitic acid, stearic acid, and the like, and more preferably a C12-18 alkane substituted with -COOH, such as lauric acid, myristic acid, palmitic acid, stearic acid, etc. is there.

  The alkane substituted with —OH means one having one or more hydrogen atoms of the alkane substituted with one or more —OH. For example, 1-10 hydrogen atoms of an alkane having 1 to 50 carbon atoms are —OH. And those substituted with 1-10. The alkane substituted with —OH is preferably an alkane having 1 to 20 carbon atoms substituted with —OH, such as methanol, ethanol, isopropanol, 2-methyl-2-propanol, butanol, pentanol, hexanol, heptanol. , Octanol, nonaol, decanol, undecanol, dodecanol, tridecanol, pentadecanol, hexadecanol, heptadecanol, octadecanol, nonadecanol, icosanol, etc., more preferably 1 to 10 carbon atoms substituted with —OH. Alkanes such as methanol, ethanol, isopropanol, 2-methyl-2-propanol, butanol, pentanol, hexanol, heptanol, octanol, nonaol, decanol and the like.

The alkane substituted with —NH ₂ means that one or more hydrogen atoms of the alkane are substituted with one or more —NH ₂ , for example, 1 to 10 hydrogen atoms of an alkane having 1 to 50 carbon atoms. those 1-10 substituted with -NH ₂ and the like. The alkane substituted with —NH ₂ is preferably an alkane having 1 to 20 carbon atoms substituted with —NH ₂ , such as methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine, heptylamine, octyl. , nonylamine, decylamine, undecylamine, dodecylamine, tetradecylamine, pentadecyl amine, hexadecyl amine, heptadecyl amine, octadecyl amine, nonadecylamine a Ikosaniruamin etc., carbon and more preferably substituted with -NH ₂ 3 to 17 alkanes such as propylamine, butylamine, pentylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, undecylamine, dodecylamine, tetradecylamine Emissions, pentadecyl amine, hexadecyl amine, a heptadecyl amine and the like, more preferably alkane been 5-15 carbon atoms substituted with -NH _2, for example pentylamine, hexylamine, octylamine, nonylamine, Decylamine, undecylamine, dodecylamine, tetradecylamine, pentadecylamine and the like, and even more preferably dodecylamine.

  The alkane substituted with —SH means one or more hydrogen atoms of the alkane substituted with one or more of —SH. For example, 1 to 10 hydrogen atoms of an alkane having 1 to 50 carbon atoms are —SH. And those substituted with 1-10. The alkane substituted with -SH is preferably an alkane having 1 to 20 carbon atoms substituted with -SH, such as methanethiol, ethanethiol, propanethiol, butanethiol, pentanethiol, hexanethiol, heptanethiol, octane. Thiol, nonanethiol, decanethiol, undecanethiol, dodecanethiol, tridecanethiol, tetradecanethiol, pentadecanethiol, hexadecanethiol, heptadecanethiol, octadecanethiol, nonadecanethiol, icosanethiol, more preferably -SH C3-C17 alkanes substituted with, for example, propanethiol, butanethiol, pentanethiol, hexanethiol, heptanethiol, octanethiol, nonanethiol , Decanethiol, undecanethiol, dodecanethiol, tridecanethiol, tetradecanethiol, pentadecanethiol, hexadecanethiol, heptadecanethiol, and the like, more preferably an alkane having 5 to 15 carbon atoms substituted with -SH, such as pentanethiol Hexane thiol, heptane thiol, octane thiol, nonane thiol, decane thiol, undecane thiol, dodecane thiol, tridecane thiol, tetradecane thiol, pentadecane thiol, and the like, and more preferably dodecane thiol.

  The alkyl group means a group in which one hydrogen atom is removed from the chain end of the alkane, and examples thereof include those having 1 to 100 carbon atoms. The alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, Octadecyl, nonadecyl, icosanyl and the like, more preferably an alkyl group having 1 to 10 carbon atoms, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, and the like, and more preferably 1-6 alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl and the like, and even more preferably methyl.

—COOH, —SH, —SOH, —SO ₂ H, —SO ₃ H, —NH ₂ , —NOH, —NO ₂ H, —OH, —SiOH, —Si (OH) ₂ , —Si (OH) ₃ , —PO ₂ H ₂ , —PO ₃ H _2, and —PO ₄ H selected from the group consisting of one or more alkyl groups substituted with one or more hydrogen atoms of the alkyl group. The above-mentioned ones are substituted, and examples thereof include hydroxymethyl, aminoethyl, 2-sulfanylethyl and the like. The substituted alkyl group is preferably 2-sulfanylethyl.

  The alkyl group substituted with —SH means a group in which one or more hydrogen atoms of the alkyl group are substituted with —SH. For example, 1 to 10 hydrogen atoms of an alkyl group having 1 to 100 carbon atoms are 1 And those substituted with -10 -SH. The -SH substituted alkyl group is preferably an alkyl group having 1 to 20 carbon atoms substituted with -SH, such as sulfanylmethyl, 2-sulfanylethyl, sulfanylpropyl, sulfanylbutyl, sulfanylpentyl, sulfanylhexyl, sulfanyl. Heptyl, sulfanyl octyl, sulfanyl nonyl, sulfanyl decyl, sulfanyl undecyl, sulfanyl dodecyl, sulfanyl tetradecyl, sulfanyl pentadecyl, sulfanyl hexadecyl, sulfanyl heptadecyl, sulfanyl octadecyl, sulfanyl nonadecyl, sulfanyl icosanyl, and the like Preferably, the alkyl group having 2 to 10 carbon atoms substituted with —SH, such as 2-sulfanylethyl, sulfanylpropyl, sulf Nirubuchiru, sulfanyl point pen chill, sulfanyl hexyl, sulfanyl heptyl, sulfanyl octyl, sulfanyl nonyl, a sulfanyl decyl, more preferably from 2 sulfanylethyl.

Alkene means an acyclic unsaturated hydrocarbon represented by the formula C _n C _2n , and examples thereof include those having 2 to 100 carbon atoms. The alkene includes a chain shape and a branched shape. The alkene is preferably an alkene having 2 to 20 carbon atoms, such as ethene, propene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, tridecene, tetradecene, pentadecene, hexadecene, heptadecene, octadecene, Nonadecene, icosene and the like, more preferably alkene having 3 to 10 carbon atoms, such as propene, butene, pentene, hexene, heptene, octene, nonene, decene, etc., more preferably alkene having 3 to 5 carbon atoms, such as Propen, butene, pentene, etc.

—COOH, —SH, —SOH, —SO ₂ H, —SO ₃ H, —NH ₂ , —NOH, —NO ₂ H, —OH, —SiOH, —Si (OH) ₂ , —Si (OH) ₃ , —PO ₂ H ₂ , —PO ₃ H ₂ , —PO ₄ H, —COO—, —CON—, —CONH—, —CONH ₂ , —S—, —SO—, —SO ₂ —, —NH— , -NO -, - O -, - SiO -, - PH -, - PH 2 -, - PO -, - POH -, - POH 2 -, - PO 2 -, - PO 2 H -, - PO 3 - _{, -PO 3 H -, - PO} 4 -, - N (-) -, - Si (O-) the alkene containing ₂ and -Si (O-) 1 or more selected from the group consisting of _3, the Meaning an alkene containing one or more of the above substituents, such as allyl alcohol, vinylamine, propenylamine, butenylamine, pentenylamine Hexenylamine, heptenylamine, octenylamine, nonenylamine, decenylamine, undecenylamine, dodecenylamine, tridecenylamine, tetradecenylamine, pentadecenylamine, hexadecenylamine, heptadecenylamine, octadecenylamine, nonadecylamine Senylamine, oleylamine, icosenylamine, nonacosenylamine, ethenethiol, propenethiol (allyl mercaptan), butenethiol, pentenethiol, hexenethiol, heptenethiol, octenethiol, nonenethiol, decenethiol, undecenethiol, dodecenethiol, Tridecene thiol, tetradecene thiol, pentadecene thiol, hexadecene thiol, heptadecene thiol, octadecene All, nonadecenethiol, icosenethiol, nonacosethiol, acrylic acid (propenoic acid), methacrylic acid (2-methylpropenoic acid), crotonic acid (trans-but-2-enoic acid), isocrotonic acid (cis- Butanoic acid), hexenoic acid, heptenoic acid, octenoic acid, nonenoic acid, decenoic acid, undecenoic acid, dodecenoic acid, tridecenoic acid, tetradecenoic acid, pentadecenoic acid, hexadecenoic acid, heptadecenoic acid, oleic acid (cis-octadeca) -9-enoic acid), elaidic acid (trans-octadeca-9-enoic acid), maleic acid (cis-butenedioic acid), fumaric acid (trans-butenedioic acid) and the like. The _{-COOH, -SH, -SOH, -SO 2} H, -SO 3 H, -NH 2, -NOH, -NO 2 H, -OH, -SiOH, -Si (OH) 2, -Si (OH) ₃ , —PO ₂ H ₂ , —PO ₃ H ₂ , —PO ₄ H, —COO—, —CON—, —CONH—, —CONH ₂ , —S—, —SO—, —SO ₂ —, —NH -, - NO -, - O -, - SiO -, - PH -, - PH 2 -, - PO -, - POH -, - POH 2 -, - PO 2 -, - PO 2 H -, - PO 3 As the alkene containing one or more selected from the group consisting of —, —PO ₃ H—, —PO ₄ —, —N (—) —, —Si (O—) ₂ and —Si (O—) ₃ , Preferred are oleylamine, allyl mercaptan, oleic acid and the like.

—COOH, —SH, —SOH, —SO ₂ H, —SO ₃ H, —NH ₂ , —NOH, —NO ₂ H, —OH, —SiOH, —Si (OH) ₂ , —Si (OH) ₃ , —PO ₂ H ₂ , —PO ₃ H _2, and —PO ₄ H are selected from the group consisting of one or more alkenes, and one or more hydrogen atoms of the alkene are substituted with one or more substituents. For example, allyl alcohol, vinylamine, propenylamine, butenylamine, pentenylamine, hexenylamine, heptenylamine, octenylamine, nonenylamine, decenylamine, undecenylamine, dodecenylamine, tridecenylamine, tetradecenylamine, pentadecenylamine Ruamine, hexadecenylamine, heptadecenylamine, octadecenylamine, nona Cenylamine, oleylamine, icosenylamine, nonacenylamine, ethenethiol, propenethiol (allyl mercaptan), butenethiol, pentenethiol, hexenethiol, heptenethiol, octenethiol, nonenethiol, decenethiol, undecenethiol, dodecenethiol, tride Senthiol, tetradecene thiol, pentadecene thiol, hexadecene thiol, heptacene thiol, octadecene thiol, nonadecene thiol, icocene thiol, nonacose thiol, acrylic acid (propenoic acid), methacrylic acid (2 -Methylpropenoic acid), crotonic acid (trans-but-2-enoic acid), isocrotonic acid (cis-but-2-enoic acid), hexenoic acid, heptenoic acid, octenoic acid, nonenoic acid, decenoic acid Undecenoic acid, dodecenoic acid, tridecenoic acid, tetradecenoic acid, pentadecenoic acid, hexadecenoic acid, heptadecenoic acid, oleic acid (cis-octadeca-9-enoic acid), elaidic acid (trans-octadeca-9-enoic acid), maleic acid ( cis-butenedioic acid) and fumaric acid (trans-butenedioic acid). The substituted alkene is preferably oleylamine, allyl mercaptan, oleic acid or the like.

An alkene substituted with one or more selected from the group consisting of —COOH, —SH, —SOH, —SO ₂ H, —SO ₃ H, —NH ₂ and —OH is one or more hydrogen atoms of the alkene. Meaning one or more substituted with the above substituents, for example, allyl alcohol, vinylamine, propenylamine, butenylamine, pentenylamine, hexenylamine, heptenylamine, octenylamine, nonenylamine, decenylamine, undecenylamine, dodecenylamine, tridecenylamine, tetra Decenylamine, pentadecenylamine, hexadecenylamine, heptadecenylamine, octadecenylamine, nonadecenylamine, oleylamine, icocenylamine, nonacosenylamine, ethenethiol, propenethiol (allyl merca Tan), butenethiol, pentenethiol, hexenethiol, heptenethiol, octenethiol, nonenethiol, decenethiol, undecenethiol, dodecenethiol, tridecenethiol, tetradecenethiol, pentadecenethiol, hexadecenethiol, hepta Decene thiol, octadecene thiol, nonadecene thiol, icosene thiol, nonacose thiol, acrylic acid (propenoic acid), methacrylic acid (2-methylpropenoic acid), crotonic acid (trans-but-2-enoic acid) ), Isocrotonic acid (cis-but-2-enoic acid), hexenoic acid, heptenoic acid, octenoic acid, nonenic acid, decenoic acid, undecenoic acid, dodecenoic acid, tridecenoic acid, tetradecenoic acid, pentadecenoic acid, hexadecenoic acid, heptadecenoic acid ,oleic acid cis- octadec-9-enoic acid), elaidic acid (trans- octadec-9-enoic acid), maleic acid (cis- butenedioic), fumaric acid (trans- butenedioic acid) and the like. The substituted alkene is preferably oleylamine, allyl mercaptan, oleic acid or the like.

The alkene substituted with -NH _2, means that one or more hydrogen atoms of the alkene is substituted with -NH _2, for example, 1 to 10 hydrogen atoms of the alkene having 1 to 50 carbon atoms -NH _And those substituted with ₂ . The alkene substituted with —NH ₂ is preferably an alkene having 2 to 30 carbon atoms substituted with —NH ₂ , such as vinylamine, propenylamine, butenylamine, pentenylamine, hexenylamine, heptenylamine, octenylamine, nonenylamine, decenylamine. , Undecenylamine, dodecenylamine, tridecenylamine, tetradecenylamine, pentadecenylamine, hexadecenylamine, heptadecenylamine, octadecenylamine, nonadecenylamine, oleylamine, icosenylamine, nonacosenylamine, etc. There, more preferably alkene been 5 to 25 carbon atoms substituted with -NH _2, for example pentenyl amine, hexenyl amine, Heputeniruamin, Okuteniruamin, Noneniruamin, decenyl Amine, undecenylamine, dodecenylamine, tridecenylamine, tetradecenylamine, pentadecenylamine, hexadecenylamine, heptadecenylamine, octadecenylamine, nonadecenylamine, oleylamine, icosenylamine, etc. preferably alkenes having 10 to 20 carbon atoms substituted with -NH _2, for example Deseniruamin, undecenyl amine, dodecenylamine, tri decenyl amine, tetradecenyl amine, pentadecenyl amine, hexadecenyl amine, heptadecenyl amine, Octadecenylamine, nonadecenylamine, oleylamine, icocenylamine and the like, and even more preferred is oleylamine.

  The alkene substituted with —COOH means that one or more hydrogen atoms of the alkene are substituted with —COOH. For example, 1 to 10 hydrogen atoms of an alkene having 1 to 50 carbon atoms are replaced with —COOH. The thing which was done is mentioned. The alkene substituted with -COOH is preferably an alkene having 2 to 30 carbon atoms substituted with -COOH, such as acrylic acid (propenoic acid), methacrylic acid (2-methylpropenoic acid), crotonic acid (trans- But-2-enoic acid), isocrotonic acid (cis-but-2-enoic acid), hexenoic acid, heptenoic acid, octenoic acid, nonenoic acid, decenoic acid, undecenoic acid, dodecenoic acid, tridecenoic acid, tetradecenoic acid, pentadecenoic acid , Hexadecenoic acid, heptadecenoic acid, oleic acid (cis-octadeca-9-enoic acid), elaidic acid (trans-octadeca-9-enoic acid), maleic acid (cis-butenedioic acid), fumaric acid (trans-butene diacid) Acid), and more preferably an alkene having 10 to 20 carbon atoms substituted with —COOH, such as decenoic acid, undecenoic acid, dodecene. , Tridecenoic acid, tetradecenoic acid, pentadecenoic acid, hexadecenoic acid, heptadecenoic acid, oleic acid, elaidic acid and the like, more preferably an alkene having 15 to 20 carbon atoms substituted with -COOH, for example, pentadecenoic acid, hexadecenoic acid, heptadecene Acid, oleic acid, elaidic acid and the like, and even more preferred is oleic acid.

  The alkene substituted with -SH means one or more hydrogen atoms of the alkene substituted with -SH, for example, 1 to 10 hydrogen atoms of an alkene having 1 to 50 carbon atoms are substituted with -SH. The thing which was done is mentioned. The alkene substituted with —SH is preferably an alkene having 2 to 30 carbon atoms substituted with —SH, such as ethene thiol, propene thiol (allyl mercaptan), butene thiol, pentene thiol, hexene thiol, heptene thiol, octene. Thiol, nonenethiol, decenethiol, undecenethiol, dodecenethiol, tridecenethiol, tetradecenethiol, pentadecenethiol, hexadecenethiol, heptadecenethiol, octadecenethiol, nonadecenethiol, ico And more preferably alkene having 2 to 20 carbon atoms substituted with —SH, such as ethene thiol, propene thiol (allyl mercaptan), butene thiol, pentene thiol, Senthiol, heptenethiol, octenethiol, nonenethiol, decenethiol, undecenethiol, dodecenethiol, tridecenethiol, tetradecenethiol, pentadecenethiol, hexadecenethiol, heptadecenethiol, octadecenethiol, Nonadecene thiol, icosene thiol, etc., more preferably alkene having 3 to 15 carbon atoms substituted with —SH, such as propene thiol (allyl mercaptan), butene thiol, pentene thiol, hexene thiol, heptene thiol, octene thiol , Nonenethiol, decenethiol, undecenethiol, dodecenethiol, tridecenethiol, tetradecenethiol, pentadecenethiol, and more preferably allyl merca It is an end.

  The alkenyl group means a group in which one hydrogen atom is removed from the chain end of the alkyne, and examples thereof include those having 2 to 100 carbon atoms. The alkenyl group is preferably an alkenyl group having 2 to 10 carbon atoms, such as ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, and more preferably an alkenyl group having 3 to 7 carbon atoms. For example, propenyl, butenyl, pentenyl, hexenyl, heptenyl, and the like, and more preferably an alkenyl group having 4 to 6 carbon atoms, such as butenyl, pentenyl, hexenyl and the like.

—COOH, —SH, —SOH, —SO ₂ H, —SO ₃ H, —NH ₂ , —NOH, —NO ₂ H, —OH, —SiOH, —Si (OH) ₂ , —Si (OH) ₃ , —PO ₂ H ₂ , —PO ₃ H _2, and —PO ₄ H selected from the group consisting of one or more alkenyl groups substituted with one or more hydrogen atoms of the alkenyl group as the substituent. This means a substituted one, and examples thereof include ethenyl alcohol and octene thiol.

Alkyne means an acyclic unsaturated hydrocarbon represented by the formula C _n C _2n-2 , and examples thereof include those having 2 to 100 carbon atoms. The alkyne includes a chain shape and a branched shape. The alkyne is preferably an alkyne having 2 to 20 carbon atoms, such as ethyne, propyne, butyne, pentyne, hexaine, heptine, octane, nonine, decaine, undecaine, dodecane, tridecane, tetradecane, pentadecane, hexadecane, heptadecane, octadecane, Nonadecane, icosine and the like, more preferably alkyne having 3 to 10 carbon atoms, such as propyne, butyne, pentine, hexaine, heptane, octane, nonine, decaine, etc., more preferably alkene having 3 to 5 carbon atoms, such as Propin, butyne, pentyne and the like.

—COOH, —SH, —SOH, —SO ₂ H, —SO ₃ H, —NH ₂ , —NOH, —NO ₂ H, —OH, —SiOH, —Si (OH) ₂ , —Si (OH) ₃ , —PO ₂ H ₂ , —PO ₃ H ₂ , —PO ₄ H, —COO—, —CON—, —CONH—, —CONH ₂ , —S—, —SO—, —SO ₂ —, —NH— , -NO -, - O -, - SiO -, - PH -, - PH 2 -, - PO -, - POH -, - POH 2 -, - PO 2 -, - PO 2 H -, - PO 3 - _{, -PO 3 H -, - PO} 4 -, - N (-) -, - Si (O-) as the alkyne containing ₂ and -Si (O-) 1 or more selected from the group consisting of _3, the The alkyne means one containing one or more of the substituents, and examples thereof include ethyne thiol and propynylamine.

—COOH, —SH, —SOH, —SO ₂ H, —SO ₃ H, —NH ₂ , —NOH, —NO ₂ H, —OH, —SiOH, —Si (OH) ₂ , —Si (OH) ₃ Alkyne substituted with one or more selected from the group consisting of —PO ₂ H ₂ , —PO ₃ H ₂ and —PO ₄ H, wherein one or more hydrogen atoms of the alkyne are substituted with one or more substituents For example, ethynethiol, propynylamine and the like can be mentioned.

The alkyne substituted with one or more selected from the group consisting of —COOH, —SH, —SOH, —SO ₂ H, —SO ₃ H, —NH ₂ and —OH includes one or more hydrogen atoms of the alkyne. Means one or more substituted with the above-mentioned substituents, and examples thereof include ethynethiol and propynylamine.

  The alkynyl group means a group obtained by removing one hydrogen atom from the chain end of the alkyne, and examples thereof include those having 2 to 100 carbon atoms. The alkynyl group is preferably an alkynyl group having 2 to 20 carbon atoms, such as ethynyl, propynyl, butynyl, pentynyl, hexaynyl, heptynyl, octaynyl, noninyl, decynyl, undecynyl, dodecynyl, tridecynyl, tetradecynyl, pentadecynyl. , Hexadecynyl, heptadecynyl, octadecynyl, nonadecynyl, icosinyl, etc., more preferably an alkynyl group having 2 to 10 carbon atoms, such as ethynyl, propynyl, butynyl, pentynyl, hexaynyl, heptynyl, octaynyl, noninyl, decynyl And more preferably an alkynyl group having 2 to 5 carbon atoms such as ethynyl, propynyl, butynyl, pentynyl and the like.

—COOH, —SH, —SOH, —SO ₂ H, —SO ₃ H, —NH ₂ , —NOH, —NO ₂ H, —OH, —SiOH, —Si (OH) ₂ , —Si (OH) ₃ , —PO ₂ H ₂ , —PO ₃ H _2, and —PO ₄ H selected from the group consisting of one or more alkynyl groups substituted with one or more hydrogen atoms of the alkynyl group as the substituent. This means one substituted as described above, and examples thereof include hydroxyethynyl.

  The alicyclic hydrocarbon has a structure in which carbon atoms are bonded in a cyclic manner and does not include the most conjugated double bonds, and examples thereof include those having 3 to 50 carbon atoms. The alicyclic hydrocarbon preferably has 3 to 20 carbon atoms, such as cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane, cycloundecane, cyclododecane, cyclotridecane. , Cyclotetradecane, cyclopentadecane, cyclohexadecane, cycloheptadecane, cyclooctadecane, cyclononadecane, cycloicosane, decahydronaphthalene and the like, more preferably those having 5 to 15 carbon atoms such as cyclopentane, cyclohexane, cycloheptane, cyclo Octane, cyclononane, cyclodecane, cycloundecane, cyclododecane, cyclotridecane, cyclotetradecane, cyclopentadecane, decahydronaphthalene, etc. The preferable carbon number of 10-15, for example cyclodecane, a cycloundecane, cyclododecane, cyclotridecane, cyclotetradecane, cyclopentadecane, decahydronaphthalene and the like, even more preferably decahydronaphthalene.

  The “aromatic hydrocarbon” part in the aromatic hydrocarbon and the alkyl-substituted aromatic hydrocarbon means an unsaturated ring hydrocarbon showing aromaticity, and examples thereof include those having 6 to 30 carbon atoms. . The aromatic hydrocarbon and aromatic hydrocarbon moiety are preferably benzene, pentalene, naphthalene, phenalene, phenanthrene and the like.

—COOH, —SH, —SOH, —SO ₂ H, —SO ₃ H, —NH ₂ , —NOH, —NO ₂ H, —OH, —SiOH, —Si (OH) ₂ , —Si (OH) ₃ , —PO ₂ H ₂ , —PO ₃ H ₂ , —PO ₄ H, —COO—, —CON—, —CONH—, —CONH ₂ , —S—, —SO—, —SO ₂ —, —NH— , -NO -, - O -, - SiO -, - PH -, - PH 2 -, - PO -, - POH -, - POH 2 -, - PO 2 -, - PO 2 H -, - PO 3 - _{, -PO 3 H -, - PO} 4 -, - N (-) -, - Si (O-) aromatic hydrocarbons containing ₂ and -Si (O-) 1 or more selected from the group consisting of ₃ Means that the aromatic hydrocarbon contains one or more of the substituents, and examples thereof include benzoic acid, benzenethiol, and aniline.

—COOH, —SH, —SOH, —SO ₂ H, —SO ₃ H, —NH ₂ , —NOH, —NO ₂ H, —OH, —SiOH, —Si (OH) ₂ , —Si (OH) ₃ , —PO ₂ H ₂ , —PO ₃ H _2, and —PO ₄ H selected from the group consisting of one or more aromatic hydrocarbons include one or more hydrogen atoms of the aromatic hydrocarbon as described above Meaning one or more substituted with a substituent, for example, benzoic acid, benzenethiol, aniline and the like.

Examples of the aromatic hydrocarbon substituted with one or more selected from the group consisting of —COOH, —SH, —SOH, —SO ₂ H, —SO ₃ H, —NH ₂ and —OH include the aromatic hydrocarbons. In which at least one hydrogen atom is substituted with one or more of the above substituents, for example, benzoic acid, benzenethiol, aniline, and the like.

  The alkyl-substituted aromatic hydrocarbon means a compound in which one or more hydrogen atoms of the aromatic hydrocarbon are substituted with the alkyl group, for example, substituted with an alkyl group having 1 to 10 carbon atoms. And aromatic hydrocarbons having 6 to 30 carbon atoms. Examples of the alkyl-substituted aromatic hydrocarbon include methylbenzene (toluene), propylpentalene, hexylnaphthalene, methylphenalene, and ethylphenanthrene, preferably substituted with an alkyl group having 1 to 6 carbon atoms. Aromatic hydrocarbons such as benzene (toluene), propylpentalene, hexylnaphthalene, methylphenalene, ethylphenanthrene, more preferably aromatic hydrocarbons substituted with alkyl groups of 1 to 3 carbon atoms such as benzene (toluene) , Propylpentalene, ethylnaphthalene, methylphenalene, ethylphenanthrene, and more preferably toluene.

—COOH, —SH, —SOH, —SO ₂ H, —SO ₃ H, —NH ₂ , —NOH, —NO ₂ H, —OH, —SiOH, —Si (OH) ₂ , —Si (OH) ₃ , —PO ₂ H ₂ , —PO ₃ H ₂ , —PO ₄ H, —COO—, —CON—, —CONH—, —CONH ₂ , —S—, —SO—, —SO ₂ —, —NH— , -NO -, - O -, - SiO -, - PH -, - PH 2 -, - PO -, - POH -, - POH 2 -, - PO 2 -, - PO 2 H -, - PO 3 - _{, -PO 3 H -, - PO} 4 -, - N (-) -, - Si (O-) alkyl-substituted aromatic containing ₂ and -Si (O-) 1 or more selected from the group consisting of ₃ Aromatic hydrocarbon means that the alkyl-substituted aromatic hydrocarbon contains one or more of the substituents, such as benzyl alcohol, phenyl vinegar An acid etc. are mentioned.

—COOH, —SH, —SOH, —SO ₂ H, —SO ₃ H, —NH ₂ , —NOH, —NO ₂ H, —OH, —SiOH, —Si (OH) ₂ , —Si (OH) ₃ As the alkyl-substituted aromatic hydrocarbon substituted with one or more selected from the group consisting of —PO ₂ H ₂ , —PO ₃ H ₂ and —PO ₄ H, the alkyl-substituted aromatic hydrocarbon In which one or more hydrogen atoms are substituted with one or more of the above-mentioned substituents, such as benzyl alcohol and phenylacetic acid.

The alkyl-substituted aromatic hydrocarbon substituted with one or more selected from the group consisting of —COOH, —SH, —SOH, —SO ₂ H, —SO ₃ H, —NH ₂ and —OH is the alkyl This means that one or more hydrogen atoms of a substituted aromatic hydrocarbon are substituted with one or more of the above substituents, and examples thereof include benzyl alcohol, phenylacetic acid, dibenzyl ketone and the like.

  The aryl group means a group obtained by removing one hydrogen atom from the aromatic hydrocarbon, and examples thereof include those having 6 to 30 carbon atoms. The aryl group is preferably phenyl, pentarenyl, naphthalenyl, phenalenyl, phenanthrenyl and the like.

—COOH, —SH, —SOH, —SO ₂ H, —SO ₃ H, —NH ₂ , —NOH, —NO ₂ H, —OH, —SiOH, —Si (OH) ₂ , —Si (OH) ₃ , —PO ₂ H ₂ , —PO ₃ H _2, and —PO ₄ H selected from the group consisting of one or more aryls substituted with one or more hydrogen atoms of the aryl group as one or more substituents This means a substituted one, and examples thereof include hydroxyphenyl.

  The alkyl-substituted aryl group means a group in which one or more hydrogen atoms of the aryl group are substituted with the alkyl group, for example, 6 to 6 carbon atoms substituted with an alkyl group having 1 to 10 carbon atoms. There are 30 aryl groups. The alkyl-substituted aryl group is preferably methylphenyl, propylpentanyl, hexylnaphthalenyl, methylphenalenyl, ethylphenanthrenyl and the like.

—COOH, —SH, —SOH, —SO ₂ H, —SO ₃ H, —NH ₂ , —NOH, —NO ₂ H, —OH, —SiOH, —Si (OH) ₂ , —Si (OH) ₃ , —PO ₂ H ₂ , —PO ₃ H _2, and —PO ₄ H selected from the group consisting of one or more alkyl-substituted aryl groups include one or more of the above alkyl-substituted aryl groups. This means one in which one or more hydrogen atoms are substituted with the above-mentioned substituents, and examples thereof include carboxyphenylmethyl, hydroxynaphthalenylethyl, sulfanylmethylphenyl and the like.

  The “heterocycle” moiety in the heterocycle and the alkyl-substituted heterocycle means a ring containing one or more atoms other than carbon atoms, and examples thereof include heterocycles containing oxygen, sulfur, nitrogen and the like. The heterocyclic ring and heterocyclic moiety are preferably thiophene, furan, pyran, xanthene, pyrrole, imidazole, pyrazole, thiazole, isoxazole, pyridine, pyrazine, pyrimidine and the like.

—COOH, —SH, —SOH, —SO ₂ H, —SO ₃ H, —NH ₂ , —NOH, —NO ₂ H, —OH, —SiOH, —Si (OH) ₂ , —Si (OH) ₃ , —PO ₂ H ₂ , —PO ₃ H ₂ , —PO ₄ H, —COO—, —CON—, —CONH—, —CONH ₂ , —S—, —SO—, —SO ₂ —, —NH— , -NO -, - O -, - SiO -, - PH -, - PH 2 -, - PO -, - POH -, - POH 2 -, - PO 2 -, - PO 2 H -, - PO 3 - _{, -PO 3 H -, - PO} 4 -, - N (-) -, - Si (O-) as heterocyclic ring containing ₂ or -Si (O-) 1 or more selected from the group consisting of _3, The heterocyclic ring means one containing one or more of the substituents, and examples thereof include carboxyl pyridine and hydroxypyrazole.

—COOH, —SH, —SOH, —SO ₂ H, —SO ₃ H, —NH ₂ , —NOH, —NO ₂ H, —OH, —SiOH, —Si (OH) ₂ , —Si (OH) ₃ , —PO ₂ H ₂ , —PO ₃ H _2, and —PO ₄ H selected from the group consisting of one or more heterocycles substituted with one or more hydrogen atoms of the heterocycle as 1 The above-mentioned ones are substituted, and examples thereof include carboxyl pyridine and hydroxypyrazole.

The heterocyclic ring substituted with one or more selected from the group consisting of —COOH, —SH, —SOH, —SO ₂ H, —SO ₃ H, —NH ₂ and —OH is one or more hydrogen atoms of the heterocyclic ring. Means one or more substituted with the above substituents, and examples thereof include carboxyl pyridine and hydroxypyrazole.

  The alkyl-substituted heterocycle means one in which one or more hydrogen atoms of the heterocycle are substituted with the alkyl group, for example, a heterocycle substituted with an alkyl group having 1 to 10 carbon atoms. Can be mentioned. The heterocyclic ring substituted with the alkyl group is preferably methylthiophene, hexylfuran, methylpyran, butylxanthene, methylpyrrole, pentylimidazole, octylpyrazole, hexylthiazole, pentylisoxazole, butylpyridine, methylpyrazine, methylpyrimidine, etc. It is.

—COOH, —SH, —SOH, —SO ₂ H, —SO ₃ H, —NH ₂ , —NOH, —NO ₂ H, —OH, —SiOH, —Si (OH) ₂ , —Si (OH) ₃ , —PO ₂ H ₂ , —PO ₃ H ₂ , —PO ₄ H, —COO—, —CON—, —CONH—, —CONH ₂ , —S—, —SO—, —SO ₂ —, —NH— , -NO -, - O -, - SiO -, - PH -, - PH 2 -, - PO -, - POH -, - POH 2 -, - PO 2 -, - PO 2 H -, - PO 3 - _{, -PO 3 H -, - PO} 4 -, - N (-) -, - Si (O-) complex which is substituted including ₂ and -Si (O-) 1 or more selected from the group consisting of ₃ As a ring, it means that the alkyl-substituted heterocycle contains one or more of the substituents, for example, carboxyl pyridine, hydroxypyrazole, etc. Can be mentioned.

—COOH, —SH, —SOH, —SO ₂ H, —SO ₃ H, —NH ₂ , —NOH, —NO ₂ H, —OH, —SiOH, —Si (OH) ₂ , —Si (OH) ₃ , —PO ₂ H ₂ , —PO ₃ H ₂ and —PO ₄ H selected from the group consisting of one or more alkyl-substituted heterocycles include one or more hydrogen atoms of the heterocycle This means one substituted with one or more substituents such as carboxyl pyridine and hydroxypyrazole.

An alkyl-substituted heterocycle substituted with one or more selected from the group consisting of —COOH, —SH, —SOH, —SO ₂ H, —SO ₃ H, —NH ₂ and —OH is one of the above heterocycles. The above hydrogen atoms are substituted with one or more of the above substituents, and examples thereof include carboxyl pyridine and hydroxypyrazole.

  The heteroaryl group means a group obtained by removing one hydrogen atom from a heterocyclic ring, and examples thereof include a heteroaryl group containing oxygen, sulfur, nitrogen and the like. The heteroaryl group is preferably thiophenyl, furanyl, pyranyl, xanthenyl, pyrrolinyl, imidazolinyl, pyrazolinyl, thiazolinyl, isoxazolinyl, pyridinyl, pyrazinyl, pyrimidinyl and the like.

—COOH, —SH, —SOH, —SO ₂ H, —SO ₃ H, —NH ₂ , —NOH, —NO ₂ H, —OH, —SiOH, —Si (OH) ₂ , —Si (OH) ₃ , —PO ₂ H ₂ , —PO ₃ H ₂ and —PO ₄ H selected from the group consisting of one or more heteroaryl groups substituted with one or more hydrogen atoms of the heteroaryl group as the substituent Is substituted with, for example, carboxylpyridinyl, hydroxypyrazolinyl and the like.

  The alkyl-substituted heteroaryl group means a group obtained by removing one hydrogen atom from an alkyl-substituted heterocycle, for example, a heteroaryl group containing oxygen, sulfur, or nitrogen substituted with an alkyl group having 1 to 10 carbon atoms. Is mentioned. The alkyl-substituted heteroaryl group is preferably methylthiophenyl, hexylfuranyl, methylpyranyl, butylxanthenyl, methylpyrrolinyl, pentylimidazolinyl, octylpyrazolinyl, hexylthiazolinyl, pentylisoxazolyl. Nyl, butylpyridinyl, methylpyrazinyl, methylpyrimidinyl and the like.

—COOH, —SH, —SOH, —SO ₂ H, —SO ₃ H, —NH ₂ , —NOH, —NO ₂ H, —OH, —SiOH, —Si (OH) ₂ , —Si (OH) ₃ , —PO ₂ H ₂ , —PO ₃ H _2, and —PO ₄ H selected from the group consisting of one or more alkyl-substituted heteroaryl groups include 1 of the above alkyl-substituted heteroaryl groups This means that one or more of the above hydrogen atoms is substituted with the above substituent, and examples thereof include methylcarboxythiophenyl and the like.

  The terpene hydrocarbon part of the terpene hydrocarbon containing one or more —OH means a hydrocarbon represented by a skeletal molecular formula of isoprene, and examples thereof include terpenes, sesquiterpenes, and diterpenes.

  The terpene hydrocarbon containing one or more —OH means a compound in which one or more hydrogen atoms of the terpene hydrocarbon are substituted with a hydroxyl group. For example, terpineol, dihydroterpineol, sobrerol, peryl alcohol, myrtenol, dihydro Examples include carveol, and terpineol is preferable.

  The halogen atom is fluorine, chlorine, bromine, iodine or the like, preferably bromine.

In the method for sintering metal nanoparticles and the method for forming a wiring on a substrate according to the present invention, the coating of the metal nanoparticles has a portion that is strongly coordinated to the surface of the metal nanoparticles, specifically, a metal A compound having a functional group having a lone electron pair for forming a coordinate bond with an atom. Examples of those having a site that strongly coordinates to the surface of such metal nanoparticles include heterocycles and alkyl-substituted heterocycles, as well as —COOH, —SH, —SOH, —SO ₂ H, —SO ₃ H. , —NH ₂ , —NOH, —NO ₂ H, —OH, —SiOH, —Si (OH) ₂ , —Si (OH) ₃ , —PO ₂ H ₂ , —PO ₃ H ₂ , —PO ₄ H, -COO -, - CON -, - CONH -, - CONH 2, -S -, - SO -, - SO 2 -, - NH -, - NO -, - O -, - SiO -, - PH -, - _{PH 2 -, - PO -,} - POH -, - POH 2 -, - PO 2 -, - PO 2 H -, - PO 3 -, - PO 3 H -, - PO 4 -, - N (-) - , Alkane, alkene, alkyne, fragrance comprising one or more selected from the group consisting of -Si (O-) ₂ and -Si (O-) ₃ 1 or more selected from the group consisting of aromatic hydrocarbons, alkyl-substituted aromatic hydrocarbons, heterocycles and alkyl-substituted heterocycles.

The coating includes a heterocycle or an alkyl-substituted heterocycle;
—COOH, —SH, —SOH, —SO ₂ H, —SO ₃ H, —NH ₂ , —NOH, —NO ₂ H, —OH, —SiOH, —Si (OH) ₂ , —Si (OH) ₃ An alkane, alkene, alkyne, aromatic hydrocarbon, alkyl-substituted aromatic hydrocarbon substituted with one or more selected from the group consisting of —PO ₂ H ₂ , —PO ₃ H ₂ and —PO ₄ H; A heterocycle or an alkyl-substituted heterocycle; a compound represented by the following formula (I); a compound represented by the following formula (II); a compound represented by the following formula (III); and the following formula (IV): It is preferably formed from one or more selected from the group consisting of the represented compounds.
R ¹ -A ¹ -R ² (I)
R ³ -A ² (R ⁴ ) -R ⁵ (II)
R ⁶ -A ³ (R ⁷ ) (R ⁸ ) -R ⁹ (III)
R ¹⁰ -A ⁴ (R ¹¹ ) (R ¹² ) (R ¹³ ) X (IV)
In the formulas (I) to (IV), R ^{1 to} R ¹³ are independently of each other an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an alkyl-substituted aryl group, a heteroaryl group, or an alkyl-substituted group. A heteroaryl group, or —COOH, —SH, —SOH, —SO ₂ H, —SO ₃ H, —NH ₂ , —NOH, —NO ₂ H, —OH, —SiOH, —Si (OH) ₂ , — Alkyl group, alkenyl group, alkynyl group, aryl group, alkyl substituted with one or more selected from the group consisting of Si (OH) ₃ , —PO ₂ H ₂ , —PO ₃ H ₂ and —PO ₄ H An aryl group, a heteroaryl group or an alkyl-substituted heteroaryl group,
A ¹ represents —COO—, —CON—, —CONH—, —CONH ₂ , —S—, —SO—, —SO ₂ —, —NH—, —NO—, —O—, —SiO—, — _{PH -, - PH 2 -,} - PO -, - POH -, - POH 2 -, - PO 2 -, - PO 2 H -, - PO 3 -, - PO 3 H- or -PO ₄ - mean ,
A ² is, -N (-) -, - Si (O-) 2 means,
A ³ means —Si (O—) ₃ ,
A ⁴ is, -N (-) ₂ - means,
X means a halogen atom.

Further, the coating, -NH ₂ alkane substituted with, -NH ₂ alkene substituted with alkene substituted with -SH, an alkane substituted with -SH, alkenes and R ¹⁰ which is substituted by -COOH —A ⁴ (R ¹¹ ) (R ¹² ) (R ¹³ ) X (IV) [wherein R ¹⁰ is an alkyl group substituted with —SH, and R ¹¹ , R ¹² and R ¹³ are alkyl groups; There, a ⁴ is -N (-) - a and, X is more preferably formed from one or more selected from the group consisting of compounds represented by a halogen atom, it is substituted with -NH ₂ Alkane having 1 to 20 carbon atoms, Alkene having 2 to 30 carbon atoms substituted with —NH ₂ , Alkene having 2 to 30 carbon atoms substituted with —SH, 1 to 20 carbon atoms substituted with —SH Alkanes, alkenes of 1 to 20 carbon atoms substituted with -COOH and R in ^{10 -A 4 (R 11) (} R 12) (R 13) X (IV) [ wherein, an alkyl group of R ¹⁰ is 1 to 6 carbon atoms which is substituted by -SH, R ^11, R ¹² , R ¹³ is an alkyl group having 1 to 6 carbon atoms, A ⁴ is —N (−) —, and X is Br]. More preferably, it is most preferably formed from one or more selected from the group consisting of dodecylamine, thiocholine bromide, allyl mercaptan, dodecanethiol, oleic acid and oleylamine.

  In the method for sintering metal nanoparticles and the method for forming a wiring on a substrate according to the present invention, a combination of the metal on which the metal nanoparticles are formed and the coating of the metal nanoparticles includes: A combination of the metal and the coating is preferable so that the surface of the metal nanoparticle is strongly coordinated. As described above, the metal nanoparticles are silver, copper, gold, platinum, rhodium, nickel, platinum-gold alloy, platinum-palladium alloy, gold-silver alloy, silver-palladium alloy, palladium-gold alloy, platinum- Gold alloy, rhodium-palladium alloy, silver-rhodium alloy, copper-palladium alloy, nickel-palladium alloy, iron-platinum alloy, iron-platinum-copper alloy, iron-platinum-tin alloy, iron-platinum-bismuth alloy and iron -Particles formed from one or more metals selected from the group consisting of platinum-lead alloys, or silver, copper, gold, platinum, rhodium, nickel, platinum-gold alloys, platinum-palladium alloys, gold-silver alloys, Silver-palladium alloy, palladium-gold alloy, platinum-gold alloy, rhodium-palladium alloy, silver-rhodium alloy, copper-palladium alloy, nickel-palladium alloy, iron-platinum alloy, -Particles having a core-shell structure formed of two or more metals selected from the group consisting of platinum-copper alloy, iron-platinum-tin alloy, iron-platinum-bismuth alloy and iron-platinum-lead alloy preferable.

  Examples of combinations of the metal on which the metal nanoparticles are formed and the coating of the metal nanoparticles include silver and dodecylamine, silver and oleylamine, silver and triethylamine, silver and laurylamine, silver and butylamine, gold and dodecanethiol, etc. Preferably silver and dodecylamine.

  In the method for sintering metal nanoparticles and the method for forming a wiring on a substrate according to the present invention, the method for producing metal nanoparticles is not limited. For example, there are a physical production method and a chemical production method. The physical method is a method of obtaining nanoparticles by pulverizing a bulk metal into small pieces. The chemical production method is a method in which metal atoms (zero valence) are taken out from a precursor such as a metal salt or a metal complex and aggregated to obtain nanoparticles.

  In the method for sintering metal nanoparticles and the method for forming a wiring on a substrate according to the present invention, the dispersion solvent is a solvent in which the coated metal nanoparticles can exist stably, specifically, metal nanoparticles and It is a low polarity solvent that does not peel off the bond with the coating. Examples of the dispersion solvent include alkanes, alkenes, alkynes, alicyclic hydrocarbons, aromatic hydrocarbons, alkyl-substituted aromatic hydrocarbons, and terpene hydrocarbons containing one or more —OH.

  The dispersion solvent preferably contains at least one selected from the group consisting of alkanes, alicyclic hydrocarbons, alkyl-substituted aromatic hydrocarbons, and terpene hydrocarbons including 1-OH. Includes one or more selected from the group consisting of 20 alkanes, alicyclic hydrocarbons having 3 to 20 carbon atoms, alkyl-substituted aromatic hydrocarbons having 1 to 6 carbon atoms, and terpene hydrocarbons including 1-OH And more preferably one or more selected from the group consisting of tetradecane, toluene, terpineol, decahydronaphthalene (decalin) and 2,2,4-trimethylpentane (isooctane).

  In the method for sintering metal nanoparticles and the method for forming a wiring on a substrate according to the present invention, the combination of the metal forming the metal nanoparticles, the coating of the metal nanoparticles, and the dispersion solvent is, for example, silver. Examples include combinations of dodecylamine and tetradecane, silver and dodecylamine and toluene, silver and oleylamine and isobutanol, silver and triethylamine and toluene, silver and laurylamine and toluene, silver and butylamine and toluene, gold and dodecanethiol and toluene, etc. , Preferably a combination of silver, dodecylamine and tetradecane, silver, dodecylamine and toluene.

  The method for producing the metal nanoparticle paste used in the method for sintering metal nanoparticles and the method for forming wiring on the substrate of the present invention is not limited, but can be performed as follows, for example.

  First, the solvent is removed from the metal nanoparticle dispersion by removing under reduced pressure. At this time, if the solvent is removed under reduced pressure after adding alkylamine to the dispersion, the coating of the metal nanoparticles can be replaced with alkylamine. The obtained residue is washed with a polar solvent having an appropriate polarity. The polar solvent having an appropriate polarity is preferably one having a polarity that does not remove the coating of the metal nanoparticles. After washing, the polar solvent having the appropriate polarity is removed by solid-liquid phase separation to obtain a residue. A desired amount of a dispersion solvent can be added to the residue to obtain a metal nanoparticle paste containing the coated metal nanoparticles and the dispersion solvent.

  About the obtained metal nanoparticle paste, metal content is 10-90 mass%, for example, Preferably it is 10-85 mass%, More preferably, it is 12-80 mass%, and a viscosity is 1-500000 mPa.s, for example. s, preferably 5 to 200,000 mPa.s. s, more preferably 10-150000 mPa.s. s.

In the method for sintering metal nanoparticles and the method for forming a wiring on a substrate according to the present invention, the polar solvent solution containing the polar solvent or solubilizing agent acting on the metal nanoparticle paste peels the coating from the metal nanoparticles. And the disperse solvent thus peeled can be dissolved. Specifically, the polar solvent or the dissolution aid has a higher affinity between the coating of the metal nanoparticle and the metal nanoparticle than the coating and the polar solvent solution containing the polar solvent or the dissolution aid. It is a polar solvent solution containing an agent. The polar solvent is, for example, selected from the group consisting of a heterocycle, an alkyl-substituted heterocycle, water, —COOH, —SH, —SOH, —SO ₂ H, —SO ₃ H, —NH ₂ and —OH. From one or more substituted alkanes, alkenes, alkynes, aromatic hydrocarbons, alkyl-substituted aromatic hydrocarbons, heterocycles and alkyl-substituted heterocycles, and compounds represented by the following formula (X) One or more polar solvents selected from the group consisting of:
R ²¹ -Y-R ²² (X)
In the formula (X), R ²¹ and R ²² are each independently an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an alkyl-substituted aryl group, a heteroaryl group or an alkyl-substituted heteroaryl group. Yes,
Y is a group represented by —CONH—, —C (═O) —, or —SO—.

The polar solvent is preferably one or more selected from the group consisting of an alkane substituted with —OH, a ketone represented by the following formula (XI), an alkane substituted with one or more —COOH, and water.
R ²¹ —C (═O) —R ²² (XI)
In the formula (XI), R ²¹ and R ²² are each independently an alkyl group.

Examples of the polar solvent include an alkane having 1 to 6 carbon atoms substituted with —OH, a ketone represented by the formula (XI) [in the formula (XI), R ²¹ and R ²² are each independently a carbon atom. More preferably one or more selected from the group consisting of alkanes having 1 to 6 carbon atoms substituted with one or more —COOH and water, methanol, ethanol, isopropanol, More preferred is a mixture of 2-methyl-2-propanol, acetone, acetic acid, acetic acid and water.

  The additive may be any one that has a function of enhancing the polarity of the polar solvent and a function of assisting dissolution of the coating. Examples thereof include polyvinyl pyrrolidone, polyvinyl alcohol, ammonia, and the like. Alcohol and ammonia are preferred.

  Examples of the polar solvent solution of the additive include an aqueous solution of polyvinyl pyrrolidone, an aqueous solution of polyvinyl alcohol, a methanol solution of polyvinyl pyrrolidone, an ethanol solution of polyvinyl pyrrolidone, an isopropanol solution of polyvinyl pyrrolidone, and 2-methyl-2-propanol of polyvinyl pyrrolidone. Examples include a solution, an acetone solution of polyvinyl pyrrolidone, and aqueous ammonia, and an aqueous solution of polyvinyl pyrrolidone, an aqueous solution of polyvinyl alcohol, a methanol solution of polyvinyl pyrrolidone, an ethanol solution of polyvinyl pyrrolidone, aqueous ammonia, and the like are preferable.

  In the method for sintering metal nanoparticles and the method for forming wiring on a substrate of the present invention, the metal on which the metal nanoparticles are formed, the coating of the metal nanoparticles, the dispersion solvent, and the polar solvent or dissolution Examples of combinations with polar solvent solutions containing adjuvants include silver and dodecylamine and tetradecane and methanol, silver and dodecylamine and toluene and methanol, silver and oleylamine and isobutanol and methanol, silver and triethylamine and toluene and methanol, silver And laurylamine and toluene and methanol, silver and butylamine and toluene and methanol, gold and dodecanethiol and toluene and methanol, and the like, preferably silver, dodecylamine, tetradecane and methanol, silver, dodecylamine, toluene and methanol And so on.

  In the method for sintering metal nanoparticles of the present invention, each step is performed as follows.

  First, a step of allowing a polar solvent solution containing a polar solvent or a solubilizing agent to act on a metal nanoparticle paste containing a coated metal nanoparticle and a dispersion solvent on the substrate is the step of causing the substrate to be the polar solvent or solubilizing aid. It can be carried out by immersing in a bath containing a polar solvent solution containing an agent or spraying the polar solvent solution containing the polar solvent or dissolution aid on the substrate.

  Since the method for sintering metal nanoparticles of the present invention does not require heating as described above, the method can be performed regardless of temperature. Accordingly, the step of applying the polar solvent or the polar solvent solution containing the solubilizing agent may be at low temperature, room temperature, or high temperature. The step of allowing the polar solvent solution containing the polar solvent or dissolution aid to act is, for example, a temperature in the range of −20 ° C. to 150 ° C., preferably a temperature in the range of 0 ° C. to 100 ° C., more preferably 10 ° C. to 50 ° C. At a temperature in the range of. The step of applying the polar solvent or the polar solvent solution containing the solubilizing agent may be performed while applying ultrasonic waves.

  In the method for sintering metal nanoparticles according to the present invention, the step of causing the polar solvent solution containing the polar solvent or dissolution aid to act includes coating the metal nanoparticles with the polar solvent solution containing the polar solvent or dissolution aid. What is necessary is just to perform for the time required for removal. The step of allowing the polar solvent solution containing the polar solvent or solubilizing agent to act can be performed, for example, for 0.1 second to 1 day, preferably 10 seconds to 2 hours, more preferably 10 seconds to 10 minutes.

  As described above, in the method for sintering metal nanoparticles according to the present invention, the material for forming the substrate is not limited. For example, the group consisting of thermoplastic resin, thermosetting resin, glass, paper, metal, silicon, and ceramics. One or more materials selected from:

  Examples of the thermoplastic resin include polyethylene, polyethylene terephthalate, polypropylene, polyvinyl chloride, polystyrene, acrylonitrile-butadiene-styrene copolymer resin, acrylonitrile-styrene copolymer resin, polycarbonate, polyacetal, polybutylene terephthalate, polyphenylene oxide, polyamide. , Polyphenylene sulfide, polysulfone, polyethersulfone, polyether-etherketone, polyarylate, aromatic polyester, aromatic polyamide, fluororesin, polyvinylidene chloride, polyvinyl alcohol, polyvinyl acetate, polyvinyl formal, polyvinyl butyral, polymethacrylic acid Examples include methyl and cellulose acetate.

  Examples of the thermosetting resin include phenol resin, urea resin, xylene resin, urea resin, melamine resin, epoxy resin, silicon resin, diallyl phthalate resin, furan resin, aniline resin, acetone-formaldehyde resin, alkyd resin, and the like. Can be mentioned.

  Examples of the metal include silver, copper, gold, platinum, rhodium, nickel, platinum-gold alloy, platinum-palladium alloy, gold-silver alloy, silver-palladium alloy, palladium-gold alloy, platinum-gold alloy, rhodium- A palladium alloy, a silver-rhodium alloy, a copper-palladium alloy, etc. are mentioned.

The ceramic means inorganic compounds such as oxides, carbides, nitrides, borides and the like. For example, alumina (Al ₂ O ₃ ), silicon nitride (SiN), silicon carbide (SiC), aluminum nitride (AlN) ), Zirconium boride (ZrB ₂ ), and the like.

  Next, the step of drying the substrate is performed to remove the polar solvent solution containing the polar solvent or the dissolution aid remaining on the substrate. The drying is performed, for example, at a temperature in the range of −20 ° C. to 150 ° C., preferably at a temperature in the range of 0 ° C. to 100 ° C., more preferably at a temperature in the range of 10 ° C. to 50 ° C.

  In the method for firing metal nanoparticles of the present invention, the thickness of the sintered metal on the substrate is, for example, 0.05 μm to 100 μm, preferably 0.1 μm to 10 μm, more preferably 0.3 μm to 5 μm. It is.

  In the method for firing metal nanoparticles of the present invention, the minimum line width / interval of the sintered metal on the substrate is, for example, 0.05 μm to 5000 μm, preferably 1 μm to 3000 μm, more preferably 50 μm to 1000 μm.

In the firing process of the metal nanoparticles of the present invention, the cross-sectional area of the post-sintering metal on a substrate, for example, 0.0025μm ² ~500000μm ^2, preferably 0.1μm ² ~30000μm ^2, more preferably 15 μm to 5000 μm ² .

In the method for firing metal nanoparticles of the present invention, the electrical resistivity of the sintered metal on the substrate is, for example, 2 × 10 ⁻⁶ Ωcm to ¹ × 10 ⁻¹ Ωcm, preferably 2 × 10 ⁻⁶ Ωcm. ˜1 × 10 ⁻³ Ωcm, more preferably 2 × 10 ⁻⁶ Ωcm to 1 × 10 ⁻⁴ Ωcm.

  The steps in the method for forming a wiring on a substrate using the metal nanoparticle sintering method of the present invention will be described in detail below.

  Using the metal nanoparticle paste containing the coated metal nanoparticles and the dispersion solvent, the step of forming a pattern to be a wiring precursor on the substrate can be performed by various coating methods such as a screen printing method, an ink jet printing method, Intaglio printing, relief printing, lithographic printing, and the like can be used.

  The step of allowing a polar solvent solution containing a polar solvent or a solubilizing agent to act on the pattern on the substrate comprises the steps of coating the metal nanoparticles and the dispersion solvent on the substrate in the method for firing metal nanoparticles of the present invention. It is the same as the step of allowing a polar solvent solution containing a polar solvent or a solubilizing agent to act on the metal nanoparticle paste containing.

  Moreover, the process of drying the said board | substrate, sintering the said metal nanoparticle, and forming a wiring is the same as the process of drying the said board | substrate in the baking method of the metal nanoparticle of the said this invention.

(Preparation Example 1)
(Nanopaste containing silver nanoparticles coated with dodecylamine and tetradecane) Preparation of metal nanoparticle paste Silver nitrate (22.1 g) and dodecylamine (48.2 g) were dissolved in acetonitrile (700 ml) and obtained The mixture was stirred at room temperature for 3 hours. The solid produced and precipitated in the mixed solution was collected by filtration, and the obtained solid was dried at 20 ° C. to obtain 7.38 g of [Ag (NH ₂ C ₁₂ H ₂₅ ) ₂ ] NO ₃ as a white powder. It was. Next, the mixture of [Ag (NH ₂ C ₁₂ H ₂₅ ) ₂ ] NO ₃ (2.0 g), dodecylamine (3.0 g) and ethanol (0.5 ml) was stirred from room temperature to 160 ° C. The mixture was heated and maintained for 300 seconds when the heating temperature reached 160 ° C. Thereafter, the mixture was naturally cooled, and stirred for 300 seconds when the temperature of the mixture reached 60 ° C. Acetone (30 ml) was added to the mixture and then the mixture was stirred for 60 seconds. After stirring was stopped and allowed to stand, the supernatant was removed from the mixture. Acetone (20 ml) was added to the resulting precipitate, and the resulting mixture was stirred for 30 seconds. After stirring was stopped and allowed to stand, the supernatant was removed from the mixture. Acetone (20 ml) was added to the resulting precipitate, and the supernatant was removed from the resulting mixture. When toluene (20 ml) was added to the obtained precipitate, the precipitate was dispersed in toluene, and a metallic blue solution was obtained. The solution was stirred at room temperature for 300 seconds, and then the solution was filtered through a glass fiber filter paper (retained particle diameter: 0.3 μm). The obtained filtrate was concentrated under reduced pressure to obtain a fine blue powder. The above operation was repeated 5 times to obtain a blue powder (0.08 g, yield: 4.0%). After adding tetradecane (0.07 ml) to the blue powder, the nanopaste (metal content: 60% by mass, viscosity) containing silver nanoparticles coated with dodecylamine and tetradecane in the title is added. 30 mPa · s) was obtained.

(Preparation Example 2)
A nanopaste containing silver nanoparticles coated with dodecylamine and toluene in the same manner as in Preparation Example 1 except that toluene (0.55 g) is used instead of tetradecane (metal content: 12.6% by mass) Got.

  A polar solvent was allowed to act on the metal nanoparticle paste produced in Preparation Example 1 on a substrate (polyethylene terephthalate) for 30 seconds at 23 ° C., and the substrate was dried at 23 ° C. for 2 hours. The electrical resistivity of the metal on the obtained substrate was measured by a four-terminal method using a low resistivity meter (trade name: Loresta CP, manufactured by Mitsubishi Chemical) and a four-probe probe (NSCP probe). The minimum line width / wiring interval was measured using a laser microscope (ultra depth color 3D shape measurement microscope VK-9510m, manufactured by KEYENCE). Table 1 below shows the results of measuring the electric resistance value with various polar solvents. In Table 1, “Good” means that electrical continuity has been confirmed, “Yes” means that electrical continuity has been confirmed but is unstable or very weak, and “No” means that electrical continuity has been confirmed. It means that it was not possible.

When the metal nanoparticle paste manufactured in Preparation Example 1 was used and ethanol was used as the polar solvent, the electrical resistivity was 8.15 × 10 ⁻⁵ Ω · cm (average value measured 10 times). The minimum line width / wiring interval was 200.03 μm / 3.0 mm. The width of the obtained metal was 208 μm (average value measured 10 times), the thickness was 0.3 μm, and the cross-sectional area was 62.4 μm ² (average value measured 10 times).

Example 2
The electrical resistance value was measured by variously changing the polar solvent in the same manner as in Example 1 except that the nanopaste produced in Preparation Example 2 was used instead of the nanopaste produced in Preparation Example 1. The results are shown in Table 1 below.

As shown in Table 1, it was confirmed from the results of Examples 1 and 2 that the metal nanoparticles can be sintered by the sintering method of the present invention. In addition, it was confirmed that the wiring can be formed on the substrate by the substrate forming method of the present invention. Further, as shown in Example 1, it was confirmed that according to the substrate forming method of the present invention, a wiring having a high resistivity of 10 ⁻⁵ level was obtained.

Example 3
The substrate (glass) on which the metal nanoparticle paste was arranged was immersed in a polar solvent at 23 ° C. As the metal nanoparticle paste, the one manufactured in Preparation Example 2 was used. Methanol was used as the polar solvent.

  The substrate was immersed in a polar solvent for 0 seconds, 30 seconds, 180 seconds, 600 seconds, 1800 seconds and 3600 seconds, respectively, and then dried at 23 ° C. for 2 hours. Changes in the metal nanoparticle paste on the substrate with the immersion time are shown in FIGS. 2 and 3 as SEM and TEM photographs.

  As shown in FIG. 2, it was confirmed that nanoparticles having a diameter of 10 nm were regularly arranged in the treated metal nanoparticle paste for 0 second, that is, untreated. Further, as the immersion time in the polar solvent became longer, the nanoparticles were grown together and confirmed to grow into particles having a size of 100 nm or more after 1 hour.

  Moreover, as shown in the said FIG. 3, when immersed in a polar solvent for 30 second, it has confirmed that nanoparticles were united and the coating | cover has begun to be removed.

Further, the electrical resistivity of the substrate was measured in the same manner as in Example 1. The immersion time and the electrical resistivity at that time are shown in FIG. From FIG. 4, it was confirmed that the electrical resistivity decreased as the immersion time increased. Further, it was confirmed that an electrical resistivity of the order of 10 ⁻⁴ was obtained even when the immersion time was only 300 seconds, and an electrical resistivity of 7.3 × 10 ⁻⁵ was obtained when the immersion time was 2 hours. Table 2 shows the decrease rate of the electrical resistance.

Example 4
The immersion was performed in the same manner as in Example 3 except that the substrate was taken out from the polar solvent and dried after 180 seconds. The electric resistance with respect to time of the substrate while being taken out from the polar solvent and dried while being immersed in the polar solvent is shown by a solid line in FIG .

  As shown in FIG. 5, it was confirmed that when the substrate was taken out after being immersed for 180 seconds and dried, the electric resistance decreased rapidly. In particular, it was confirmed that the electrical resistance began to decrease even during the immersion, the coating of the metal nanoparticles was peeled off, the electrical resistance further decreased during the drying process, and the sintering proceeded.

Comparative Example 1
It carried out like Example 4 except not using a metal nanoparticle paste. A graph of electrical resistance against time of the substrate while it is taken out from the polar solvent and dried while immersed in the polar solvent is shown by a dotted line in FIG. The electrical resistance during immersion in a polar solvent is a measurement of the electrical resistance of methanol. Immediately after entering the drying process, methanol evaporates, confirming a rapid increase in electrical resistance.

  It can also be applied to high-density circuit formation.

It is the schematic diagram which showed the state of the metal nanoparticle paste on a board | substrate. It is a SEM photograph of the metal nanoparticle paste in Example 3, and the metal on a board | substrate. It is a TEM photograph of the metal nanoparticle paste in Example 3, and the metal on a board | substrate. It is a graph which shows the relationship between the immersion time in Example 3, and an electrical resistivity. It is a graph which shows the relationship between the immersion time in Example 4, and drying time, and an electrical resistance.

Explanation of symbols

1 Metal 2 Coating 3 Dispersing solvent 4 Metal nanoparticle paste 5 Substrate

Claims (14)

A method for sintering metal nanoparticles, the method comprising:
A step of allowing a polar solvent solution containing a polar solvent or a solubilizing agent to act on a metal nanoparticle paste containing a coated metal nanoparticle and a dispersion solvent on the substrate; and drying the substrate.
The coating of the metal nanoparticles, heterocyclic and is heterocyclic and alkyl-substituted, -COOH, -SH, -SOH, -SO 2 H, -SO 3 H, -NH 2, -NOH, -NO 2 H, —OH, —SiOH, —Si (OH) ₂ , —Si (OH) ₃ , —PO ₂ H ₂ , —PO ₃ H ₂ , —PO ₄ H, —COO—, —CON—, —CONH—, — _{CONH 2, -S -, - SO} -, - SO 2 -, - NH -, - NO -, - O -, - SiO -, - PH -, - PH 2 -, - PO -, - POH -, - _{POH 2 -, - PO 2 -} , - PO 2 H -, - PO 3 -, - PO 3 H -, - PO 4 -, - N (-) -, - Si (O-) 2 and -Si (O -) Alkane, alkene, alkyne, aromatic hydrocarbon, alkyl-substituted aromatic hydrocarbon, compound containing at least one selected from the group consisting of ₃ Formed from one or more selected from the group consisting of a prime ring and an alkyl-substituted heterocycle;
The step of allowing the polar solvent solution containing the polar solvent or dissolution aid to act is performed at a temperature in the range of −20 ° C. to 100 ° C .;
The step of drying the substrate is performed at a temperature in the range of −20 ° C. to 100 ° C . ;
The polar solvent is an alkane having 1 to 6 carbon atoms substituted with -OH, formula (XI):
R ²¹ —C (═O) —R ²² (XI)
[In the formula (XI), R ²¹ and R ²² are each independently an alkyl group having 1 to 6 carbon atoms], 1 to 6 carbon atoms substituted with one or more —COOH A method which is one or more selected from the group consisting of alkanes and water .   The metal nanoparticles are silver, copper, gold, platinum, rhodium, nickel, platinum-gold alloy, platinum-palladium alloy, gold-silver alloy, silver-palladium alloy, palladium-gold alloy, platinum-gold alloy, rhodium- Palladium alloy, silver-rhodium alloy, copper-palladium alloy, nickel-palladium alloy, iron-platinum alloy, iron-platinum-copper alloy, iron-platinum-tin alloy, iron-platinum-bismuth alloy and iron-platinum-lead alloy Particles formed from one or more metals selected from the group consisting of: silver, copper, gold, platinum, rhodium, nickel, platinum-gold alloys, platinum-palladium alloys, gold-silver alloys, silver-palladium alloys, Palladium-gold alloy, platinum-gold alloy, rhodium-palladium alloy, silver-rhodium alloy, copper-palladium alloy, nickel-palladium alloy, iron-platinum alloy, iron-platinum-copper alloy 2. The method according to claim 1, wherein the particles have a core-shell structure formed from two or more metals selected from the group consisting of iron-platinum-tin alloys, iron-platinum-bismuth alloys, and iron-platinum-lead alloys. .   The dispersion solvent is one or more selected from the group consisting of alkanes, alkenes, alkynes, alicyclic hydrocarbons, aromatic hydrocarbons, alkyl-substituted aromatic hydrocarbons, and terpene hydrocarbons containing one or more —OH. The method according to claim 1 or 2, comprising: The method according to claim 2 or 3 , wherein the metal nanoparticles are particles formed from silver .   The method according to any one of claims 1 to 4, wherein the solubilizing agent is one or more selected from the group consisting of polyvinylpyrrolidone and polyvinyl alcohol.   The method according to claim 1, wherein the substrate is formed from one or more materials selected from the group consisting of thermoplastic resin, thermosetting resin, glass, paper, metal, silicon, and ceramics. The electrical resistivity of the sintered metal on the substrate is 2 × 10 ^-6 ~ 1x10 ^-Four The method according to claim 1, which is Ωcm. A method of forming wiring on a substrate, the method comprising:
Using a metal nanoparticle paste containing coated metal nanoparticles and a dispersion solvent, forming a pattern to be a wiring precursor on a substrate;
A step of allowing a polar solvent solution containing a polar solvent or a solubilizing agent to act on the pattern on the substrate;
And drying the substrate to sinter the metal nanoparticles to form a wiring,
The coating of the metal nanoparticles, heterocyclic and is heterocyclic and alkyl-substituted, -COOH, -SH, -SOH, -SO 2 H, -SO 3 H, -NH 2, -NOH, -NO 2 H, —OH, —SiOH, —Si (OH) ₂ , —Si (OH) ₃ , —PO ₂ H ₂ , —PO ₃ H ₂ , —PO ₄ H, —COO—, —CON—, —CONH—, — _{CONH 2, -S -, - SO} -, - SO 2 -, - NH -, - NO -, - O -, - SiO -, - PH -, - PH 2 -, - PO -, - POH -, - _{POH 2 -, - PO 2 -} , - PO 2 H -, - PO 3 -, - PO 3 H -, - PO 4 -, - N (-) -, - Si (O-) 2 and -Si (O -) Alkane, alkene, alkyne, aromatic hydrocarbon, alkyl-substituted aromatic hydrocarbon, compound containing at least one selected from the group consisting of ₃ Formed from one or more selected from the group consisting of a prime ring and an alkyl-substituted heterocycle;
The step of allowing the polar solvent solution containing the polar solvent or dissolution aid to act is performed at a temperature in the range of −20 ° C. to 100 ° C .;
The step of drying the substrate is performed at a temperature in the range of −20 ° C. to 100 ° C . ;
The polar solvent is an alkane having 1 to 6 carbon atoms substituted with -OH, formula (XI):
R ²¹ —C (═O) —R ²² (XI)
[In the formula (XI), R ²¹ and R ²² are each independently an alkyl group having 1 to 6 carbon atoms], 1 to 6 carbon atoms substituted with one or more —COOH A method which is one or more selected from the group consisting of alkanes and water . The metal nanoparticles are silver, copper, gold, platinum, rhodium, nickel, platinum-gold alloy, platinum-palladium alloy, gold-silver alloy, silver-palladium alloy, palladium-gold alloy, platinum-gold alloy, rhodium- Palladium alloy, silver-rhodium alloy, copper-palladium alloy, nickel-palladium alloy, iron-platinum alloy, iron-platinum-copper alloy, iron-platinum-tin alloy, iron-platinum-bismuth alloy and iron-platinum-lead alloy Particles formed from one or more metals selected from the group consisting of: silver, copper, gold, platinum, rhodium, nickel, platinum-gold alloys, platinum-palladium alloys, gold-silver alloys, silver-palladium alloys, Palladium-gold alloy, platinum-gold alloy, rhodium-palladium alloy, silver-rhodium alloy, copper-palladium alloy, nickel-palladium alloy, iron-platinum alloy, iron-platinum-copper alloy Iron - platinum - tin alloy, an iron - platinum - bismuth alloy and iron - platinum - The method of claim 8 wherein particles having a core-shell structure formed of two or more metals selected from the group consisting of lead alloy . The dispersion solvent is one or more selected from the group consisting of alkanes, alkenes, alkynes, alicyclic hydrocarbons, aromatic hydrocarbons, alkyl-substituted aromatic hydrocarbons, and terpene hydrocarbons containing one or more —OH. 10. The method according to claim 8 or 9 , comprising: The method according to claim 9 or 10 , wherein the metal nanoparticles are particles formed from silver . The method according to any one of claims 8 to 11 , wherein the solubilizer is one or more selected from the group consisting of polyvinylpyrrolidone and polyvinyl alcohol. The method according to any one of claims 8 to 12 , wherein the substrate is formed from one or more materials selected from the group consisting of thermoplastic resin, thermosetting resin, glass, paper, metal, silicon and ceramics. The electrical resistivity of the sintered metal on the substrate is 2 × 10 ^-6 ~ 1x10 ^-Four The method according to claim 8, which is Ωcm.