KR20080001567A - Novel metal nanoparticle and formation method of conducting pattern using the same - Google Patents

Abstract

Novel metal nanoparticles and a conductive pattern forming method using the nanoparticle are provided to obtain film having improved conductivity which is controlled as desired and to form easily conductive film or patterns by means of printing method. A metal nanoparticle has self-assemble monolayer consisting of a compound of formula 1 represented by X-Y, wherein X is NC, NH2, COOH or phosphate, and Y is monovalent organic group having 1-30 carbon atoms or polyvalent organic group having 1-30 carbon atoms having at least one substituent selected from a group consisting of OH, NH2, NO2, methoxy, ethoxy, phenoxy, halogen atom, heterosulfur group, heteroamine, oxadiazol and triphenylamine copper phthalocyanin. The other metal nanoparticle has self-assemble monolayer consisting of a compound of formula 2 represented by X-Z, wherein X is SH, NC, NH2, COOH or phosphate, and Z is -(CH2)n-Si(OR)R1R2, in which R1 and R2 are independently CH3 or OR, R is alkyl group having 1-20 carbon atoms, and n is integer of 1-10. The conductive pattern forming method comprises steps of: i) printing a composition comprising the metal nanoparticles having self-assemble monolayer on a substrate for patterning; and ii) drying the substrate. The dried substrate is optionally calcined at 150-400deg.C for 1-30 minutes.

Description

Novel metal nanoparticles and formation method of conducting pattern using the same

1 schematically shows the structure of a metal nanoparticle according to an embodiment of the present invention,

Figure 2 schematically shows the structure of the metal nanoparticles according to another embodiment of the present invention.

The present invention relates to a novel metal nanoparticles and a method for forming a conductive pattern using the same, and more particularly, to a surface, a siol group (-SH), an isocyanide group (-CN), an amino group (-NH ₂ ) as a linker. ), At least one metal nanoparticle having a self assembled monolayer composed of a predetermined compound including a carboxylate group (-COO) or a phosphate group is dispersed in an organic solvent and then patterned by printing. A method of forming a pattern.

Materials with nano-sized molecular structure exhibit various electrical, optical, and biological properties according to the spatial structure and order in one, two, and three dimensional spaces. Research on nanoparticles is being actively conducted worldwide. Among nanoscale materials, especially metal nanoparticles, they are widely used because they have a large surface area when the metal becomes nano sized in bulk and only a small number of atoms are present in the nanoparticles. Red, electrical, photoelectric and magnetic properties [Science, 256 , 1425 (1992) and Colloid Polymer. Sci. 273 , 101 (1995). In addition, since the metal nanoparticles having conductivity through an electric conduction mechanism such as charge transfer or electron transfer have a very large specific surface area, the film or pattern including the nanoparticles may be a small amount of nanoparticles. Even if it contains particles, it can have high conductivity, and if the particle size is adjusted to 3 to 15 nm to increase the packing density, charge transfer at the interface between metals becomes easier, thereby increasing the conductivity. .

On the other hand, research into a highly conductive film or pattern made of a variety of materials according to the development in the electronics industry, when using the metal nanoparticles, without a high vacuum or high temperature sputtering or etching process, etc. Not only can the film or pattern of FIG. Be prepared, there is an advantage in that the conductive pattern can be manufactured by controlling the particle size to be transparent to visible light. However, there is a difficulty in controlling and arranging the microparticles in order to apply the metal nanoparticles to a film or a pattern.

As one of the methods for the effective arrangement of the metal nanoparticles, a method using a self assembled monolayer is known. The magnetic molecular assembly layer is a molecular arrangement of a compound having a functional group having a chemical affinity with a specific metal on the metal nanoparticles, a structure capable of controlling the thickness of 10 to 40 nm. In this regard, Paul E. Laibinis et al. Reported an example in which a magnetic molecular assembly layer was formed by arranging n-alkanethiol on a metal surface [J. Am. Chem. Soc. 113 , 7152 (1991)], Yu-Tai Tao has added alkanoic acid, dialkyl disulfides and dialkyl sulfides on metal surfaces such as gold, silver, copper and aluminum. It has been reported an example of the arrangement to form a magnetic molecular assembly layer [J. Am. Chem. Soc. 115 , 4350 (1993).

However, in the case of using the metal nanoparticles including the known magnetic molecular assembly layer, it is difficult to control the spatial regularity or molecular orientation, instability of the metal nanoparticles in the thin film, defects, surface structure changes ( Due to problems such as surface ordering control and aggregation, a large area of film or pattern cannot be easily manufactured, and its commercial use is limited. Line widths that can be realized by forming a pattern by a photolithography process usually There is a problem that it is difficult to manufacture this limited and very fine pattern.

Therefore, there is an urgent need in the art for the development of new types of self-assembling nanostructures that can easily form large-area films or ultrafine patterns by simple printing processes using metal nanoparticles. It is becoming.

The present inventors earnestly studied to solve the above problems, and as a result, on the surface, as a linker, a siol group (-SH), an isocyanide group (-CN), an amino group (-NH ₂ ), a carboxylate group (-COO), Alternatively, when metal nanoparticles having a self assembled monolayer formed of a predetermined compound including a phosphate group are used, the metal nanoparticles can be easily arranged over a large area, and sputtered separately by a conventional printing process. It has been confirmed that a conductive pattern including metal nanoparticles can be formed without a process such as etching or photolithography, and has led to the present invention.

After all, the present invention is to provide a new metal nanoparticles and a pattern forming method using the same that can easily form a large area film or pattern by a printing process.

One aspect of the present invention for achieving the above object is a siol group (-SH), isocyanide group (-CN), amino group (-NH ₂ ), carboxylate group (-COO), as a linker on the surface, Or it relates to a metal nanoparticle formed with a self assembled monolayer consisting of a predetermined compound containing a phosphate group and a composition thereof.

In this case, the predetermined compound is a monovalent or polyvalent organic having an isocyanide group (-CN), an amino group (-NH ₂ ), a carboxylate group (-COO), or a linker of phosphate group having 1 to 30 carbon atoms. An organic substance connected to the group; A linker of a siol group (-SH), an isocyanide group (-CN), an amino group (-NH ₂ ), a carboxylate group (-COO), or a phosphate group is a compound connected to a group containing an alkoxy silyl group.

Another aspect of the invention relates to a composition comprising at least one of the metal nanoparticles described above, an organic solvent, and, if desired, at least one of conductive or nonconductive polymers.

Another aspect of the invention relates to a pattern forming method using the composition.

Hereinafter, with reference to the accompanying drawings will be described the present invention in more detail.

The metal nanoparticle of the present invention is a monovalent or polyvalent organic compound having 1 to 30 carbon atoms, including an isocyanide group (-CN), an amino group (-NH ₂ ), a carboxylate group (-COO), or a phosphate group as a linker. matter; Or a compound in which an alkoxy silyl group is introduced while including a functional group such as a siol group or the isocyanide group as a linker has a structure in which a magnetic molecule assembly layer is formed on the surface of the metal nanoparticle, Or as in FIG. 2.

,

및

으로 이루어진 군으로부터 선택되는 하나 이상을 포함할 수 있는 탄소수 1 내지 30의 1가 또는 2가 이상의 유기기, 보다 바람직하게는 1가 또는 2가 내지 5가의 유기기이며,In Figure 1, M is a metal nanoparticle; X is NC, NH, COO, or phosphate; The spacer is a monovalent organic group having 1 to 30 carbon atoms or OH, NH ₂ , NO ₂ , methoxy, ethoxy, phenoxy, halogen atom, hetero sulfur group, hetero amine, oxadiazole, triphenylamine, A polyvalent organic group having 1 to 30 carbon atoms having at least one substituent selected from the group consisting of copper phthalocyanine and carbazole, preferably -CONH-, -COO-, -CO- _, -CH _2- , -Si in the middle -, Bis- (porphyrin),

,

And

It is a monovalent or divalent or more organic group of 1 to 30 carbon atoms which may include one or more selected from the group consisting of, more preferably monovalent or divalent to pentavalent organic group,

In Figure 2, M is a metal nanoparticle; X is S, NC, NH, COO, or phosphate; Alkoxy silyl spacers are-(CH ₂ ) _n -Si (OR) R ₁ R ₂ , wherein R ₁ and R ₂ are each independently CH ₃ or OR, and R is C 1-20 Alkyl group, n is an integer from 1 to 10), preferably-(CH ₂ ) _n -Si (OR) ₃ or — (CH ₂ ) _n —Si (OR) (CH ₃ ) ₂ , wherein R is an alkyl group having 1 to 10 carbon atoms and n is an integer of 1 to 6;

The metal nanoparticle of the present invention having the structure of FIG. 1 has an isocyanide group (-CN), an amino group (-NH ₂ ), a carboxylate group (-COO), or phosphate as a linker on the surface of the metal nanoparticle. It can be prepared by forming a magnetic molecule assembly layer with an organic material of formula (1) having a group, that is, isocyanide compound, amine compound, carboxylate compound or phosphate compound,

[Formula 1]

X-Y

Where

X is NC, NH ₂ , COOH, or phosphate,

,

및

으로 이루어진 군으로부터 선택되는 하나 이상을 포함할 수 있는 탄소수 1 내지 30의 1가 또는 2가 이상의 유기기, 보다 바람직하게는 1가 또는 2가 내지 5가의 유기기이다.Y is a monovalent organic group having 1 to 30 carbon atoms or OH, NH ₂ , NO ₂ , methoxy, ethoxy, phenoxy, halogen atom, hetero sulfur group, hetero amine, oxadiazole, triphenylamine copper phthalocyanine and carba A polyvalent organic group having 1 to 30 carbon atoms having at least one substituent selected from the group consisting of sol, preferably -CONH-, -COO-, -CO- _, -CH _2- , -Si-, bis- (Porphyrin) [bis- (porphyrin)],

,

And

It is a C1-C30 monovalent or divalent organic group which may contain 1 or more selected from the group which consists of, More preferably, it is a monovalent or divalent to pentavalent organic group.

The metal nanoparticles of the present invention having the structure of FIG. It can be prepared by forming a molecular assembly layer.

[Formula 2]

X-Z

Where

X is SH, NC, NH ₂ , COOH, or phosphate,

Z is — (CH ₂ ) _n —Si (OR) R ₁ R ₂ , wherein R ₁ and R ₂ are each independently CH ₃ or OR, R is an alkyl group having 1 to 20 carbon atoms, and n is 1 To an integer from 10 to), preferably -(CH ₂ ) _n -S _i (OR) ₃ or — (CH ₂ ) _n —Si (OR) (CH ₃ ) ₂ , wherein R is an alkyl group having 1 to 10 carbon atoms and n is an integer of 1 to 6;

At this time, the metal nanoparticles used in the present invention is not particularly limited, but gold, silver, copper having a diameter of 1 to several hundred nm, preferably 1 to 100 nm, more preferably 1 to 30 nm. Metal nanoparticles of palladium, or platinum.

In addition, examples of the compound represented by Chemical Formula 1 are not particularly limited, but are known as isocyanide-based compounds that are known to readily coordinate through a sigma bond with a metal [Langumir, 14, 1684, (1998)]. Examples of compounds usable in the invention include butyl isocyanide, tert-butyl isocyanide, 1,1,3,3-tetramethylbutyl isocyanide (1,1, 3,3-tetramethylbutyl isocyanide, 1,6-diisocyanohexane, cyclohexyl isocyanide, cyanomethyl N, N-dimethyldithiocarbamate , N-dimethyldithiocarbamate), 1-cyano-N-methylthioformamide, benzyl cyanide, 2-naphthylacetonitrile, 4- 4-phenylbutyronitrile, 3-anilinopropioni 3-anilinopropionitirle, 3- (benzylamino) propionitrile [3- (benzylamino) propionitrile], 2-methylbenzyl cyanide, 2-fluorophenylacetonitrile , 2-chlorobenzyl cyanide, 2-bromophenylacetonitrile, 3-chlorobenzylcyanide, (3-methoxyphenyl) -acetonitrile [ (3-methoxyphenyl) -acetonitrile], 3-phenoxyphenylacetonitrile, 1,3-phenylenediacetonitrile, 4-hydroxybenzyl cyanide cyanide), (4-methoxyphenyl) acetonitrile, 4-aminobenzyl cyanide, 4-nitrophenylacetonitrile, 4-nitrophenylacetonitrile, 4'-chloro 2-cyanoacetanilide (4'-chloro-2-cyanoacetanilide), 4-cyanophenol, 4-biphenylcarboni 4-biphenylcarbonitrile, 4'pentyl-4-biphenylcarbonitrile, 4'hexyl-4-biphenylcarbonitrile, 4 ' -Hydroxy-4-biphenylcarbonitrile, 9-anthracenecarbonitrile, and the like; Amine compounds include aniline, 4-ethylaniline, 4-cyclohexylaniline, 2,3-diaminophenol, 3,4- difluoroaniline, 4-aminobiphenyl, 9-aminophenanthrene, 1-aminoindan, 3,5-dimethoxybenzylamine, 3,4,5-trimethoxybenzylamine, 1,9-diaminononane, 1,10-diaminononane ), 1,12-diaminododocane (1,12-diaminonododecane), tetraethylenepentaamine (tetraethylenepentamine), 1-adamantaneamine (1-adamantanamine) and the like. The carboxylate compounds include octanoic acid, undecanoic acid, undecanodioic acid, ethoxyacetic acid, and cycloheptane carboxylic acid. ), 1-adamantaneacetic acid (1-adamantaneacetic acid), phenylacetic acid (phenylacetic acid), 6-phenylhexanoic acid (6-phenylhexanoic acid), 4-fluorophenylacetic acid (4-fluorophenylacetic acid) acid), 4-hydroxycinnamic acid, salicylic acid, 4-tert-butylbenzoic acid, 1,3,5-benzene tree Carboxylic acid (1,3,5-benzenetricarboxylic acid), 2,5-dinitrobenzoic acid, 3,5-di-tert-butylbenzoic acid (3,5- di-tert-butylbenzoic acid), gallic acid, 4,4'-biphenyldicarboxylic acid, 1-naphtholic acid (1-naphtholic acid), 9-fluorenecarboxylic acid, 1-pyrenecarboxylic acid, carbobenzooxyglycine, 6- (carbenzyloxyamino ) -Caproic acid [6- (carbobenzyloxyamino) -caproic acid]; Phosphate compounds include diphenyl phosphite, dibenzyl phosphite, bis (4-nitrobenzyl) phosphate [Bis (4-nitrobenzyl) phosphite], and dimethyl (3-phenoxyacetonyl) Phosphate [dimethyl (3-phenoxyacetonyl) phosphate], triphenyl phosphite, benzyl diethyl phosphite, phenyl phosphinic acid, ethyl phenyl phosphate , Bis (4-methoxyphenyl) phosphonic acid, dimethyl phenylphosphonite, diethyl phenylphosphonite, diphenyl phosphonic acid, diphenyl phosphonic acid, phenyl phosphonic Phenyl phosphonic acid, (4-aminobenzyl) phosphonic acid [4-aminobenzyl] phosphonic acid, diphenyl methyl phosphate, 1-naphthyl phosphate, 1,1 '-Binaphthyl-2,2'-dil Id include hydrogen phosphate (1,1'-binaphthyl-2,2'-diyl hydrogen phosphate).

On the other hand, as the compound represented by Formula 2, N- [3- (trimethoxysilyl) propylethylene diamine] [N- (3- (trimethoxysilyl) propylethylene diamine], 3-aminopropylmethyldimethoxysilane (3- aminopropylmethyldimethoxysilane, mercaptomethylmethyldiethoxysilane, m-aminophenyltrimethoxysilane, 4-aminobutyltriethoxysilane, N- (2-aminoethyl) 3-aminopropylmethyldimethoxysilane [N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane], 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane (3- mercaptopropylmethyldimethoxysilane) 3-mercaptopropyltriethoxysilane, 4-triethoxysilyl) butyronitrile [4- (triethoxysilyl) butyronitrile], 3- (triethoxysilyl) propylthioisocyanate [3- (triethoxysilyl) propylthiocyana te], but are not necessarily limited thereto.

Specifically, the metal nanoparticles of the present invention are obtained by first obtaining a general metal nanoparticles by a known method, and then the metal nanoparticles, together with the compound represented by the formula (1) or (2) in a suitable organic solvent It can form by disperse | distributing and stirring for a fixed time. At this time, the metal nanoparticles can be obtained by all known methods, and is not particularly limited, for example, the aqueous solution containing the metal ions to be obtained in the form of nanoparticles, if necessary for the stability of the particles In the presence of a surfactant such as sodium oleate, it is prepared by reduction with a reducing agent such as citrate, EDTA, NaBH4, or the like, or a metal hydrazine carboxylate [M (N ₂ H ₃₎ of the metal to be obtained. COO) ₂ .2H ₂ O (M = Mg, Ca, Mn, Fe, Co, Ni, Cu)] can be prepared by refluxing the aqueous solution at 70 to 90 ℃, preferably 80 ℃.

In addition to the above-described method, the compound of formula 1 or 2 having the above-described thiol group (-SH), isocyanide group (-CN), amino group (-NH ₂ ), carboxylate group (-COO), or phosphate group The organic solution of was reacted with an aqueous solution containing the metal ions to be obtained under a phase transfer catalyst to obtain a dispersion of metal particles surrounded by the compound molecules of Formula 1 or Formula 2 in the organic solution layer, and the dispersion was treated with a reducing agent to form magnetic molecules. After the metal nanoparticles including the granulation layer are precipitated, the metal nanoparticles in the state where the magnetic molecular granulation layer is formed may be directly obtained by centrifugation.

At this time, the conductivity of the film or pattern manufactured using the nanoparticles can be adjusted to a desired range by appropriately adjusting the size of the nanoparticles by controlling the reaction conditions and the concentration of the material used during the manufacturing process of the metal nanoparticles. have.

These metal nanoparticles of the present invention having the structure of FIG.

That is, the present invention provides a metal nanoparticle composition comprising the metal nanoparticle of FIG. 1 and the metal nanoparticle of FIG. 2. In this case, it is advantageous because it can impart better uniformity, packing density, adhesiveness and conductivity to the film.

In this case, the metal nanoparticles of FIG. 1 and the metal nanoparticles of FIG. 2 may each be selected and mixed in one or more kinds in an appropriate amount by those skilled in the art, and preferably 1: in terms of conductivity and adhesion. 1 to 10: 1, more preferably 1: 1 to 5: 1 may be used in combination, but is not necessarily limited thereto.

The present invention further provides at least one metal nanoparticle; Organic solvents; And it provides a pattern forming composition comprising at least one polymer of the conductive or non-conductive polymer, if necessary.

The metal nanoparticles used in the present invention are as described above as one or more nanoparticles of the metal nanoparticles of FIG. 1 or the metal nanoparticles of FIG. 2, and the amount of the metal nanoparticles used in the composition is determined by Depending on the conductivity, the viscosity of the composition and the coating method, preferably 0.01 to 80% by weight of the total composition, more preferably 0.5 to 50% by weight, still more preferably 1 to 20% by weight, but is not limited thereto. It doesn't work. At this time, when using more than 80% by weight of the metal nanoparticles, non-uniform problems may occur during coating and printing.

Organic solvents usable in the present invention include all organic solvents used in the technical field to which the present invention belongs, and in consideration of solubility, dispersibility and ease of film formation, propylene glycol methyl ether acetate (Propylene glycol methyl) ether acetate: PGMEA), dipropylene glycol methyl ether acetate, ethylene glycol mono ethyl ether, 2-methoxyethanol, dimethylformamide (DMF), 4-hydroxy-4-methyl-2-pentanone (PT), meth The oxypropyl acetate, ethyl-3-ethoxypropionate, cyclohexanone, and the like may be used alone or in combination of two or more, but is not necessarily limited thereto.

As described above, in the case of the pattern forming composition according to the present invention, one or more polymers among conductive or non-conductive polymers may be further included as a binder. In this case, uniformity and various functionalities may be imparted to the coating. It can be advantageous.

Examples of conductive polymers that can be used include polyacetylene (PA), polythiophene (PT), poly (3-alkyl) thiophene (P3AT), polypyrrole: PPY ), Polyisothianapthelene (PITN), polyethylene dioxythiophene (PEDOT), polyparaphenylene vinylene (PPV), poly (2,5-dialkoxy) paraphenylene vinylene [ poly (2,5-dialkoxy) paraphenylene vinylene], polyparaphenylene (PPP), polyparaphenylene sulphide (PPS), polyheptadiyne (PHT), poly (3-hexyl) theo Pens [poly (3-hexyl) thiophene: P3HT], polyaniline [polyaniline: PANI], and mixtures of two or more thereof. The number average molecular weight of the conductive polymer is preferably 1,000 to 30,000. The conductive polymer is used in a ratio of 1 to 15 parts by weight, preferably 3 to 10 parts by weight, per 100 parts by weight of the metal nanoparticles. In this case, a commercially available epoxy compound having an epoxy acrylate derivative and glycidyl ether group can be overcoated for the firmness of the coating.

Examples of non-conductive polymers usable in the present invention include polyester, polycarbonate, polyvinyl alcohol, polyvinyl butyral, polyacetal, polyarylate, polyamide, polyamideimide, polyetherimide, polyphenylene ether, poly Phenylene sulfide, polyether sulfone, polyether ketone, polyphthalamide, polyether nitrile, polyether sulfone, polybenzimidazole, polycarbodiimide, polysiloxane, polymethyl methacrylate, polymethacrylamide, nitrile rubber, Acrylic rubber, polyethylene tetrafluoride, epoxy resin, phenol resin, melamine resin, urea resin, polybutene, polypentene, ethylene-propylene copolymer, ethylene-butene-diene copolymer, polybutadiene, polyisoprene, ethylene-propylene -Diene copolymer, butyl rubber, polymethylpentene, polystyrene, styrene-butadiene copolymerization , Hydrogenated (hydrogenated) styrene-butadiene copolymer, hydrogenated polyisoprene, hydrogenated polybutadiene and one or a mixture of two or more thereof, but are not also limited to this. The number average molecular weight of the nonconductive polymer is preferably 3,000 to 30,000 in consideration of solubility and printability. The nonconductive polymer is used in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the metal nanoparticles.

Further, the composition for forming a pattern according to the present invention may be a defoamer, a viscosity modifier, a dye, a filler, a flame retardant, a humectant, a dispersant, or the like, depending on the use of printing and a thin film within a range that does not impair the object of the present invention. It is also possible to further include one or more kinds of additives. At this time, each of the additives can be used without limitation known materials known in the art, the amount of the metal nanoparticles may be used in an appropriate amount in consideration of the performance, film thickness, use, etc. of each additive. Preference is given to 0.01 to 15 parts by weight per 100 parts by weight.

If the composition according to the present invention is uniformly printed and patterned on a substrate, and then dried and / or calcined under a predetermined condition, the conductive film is not subjected to a separate sputtering, etching or photolithography process, and the like in a simple manner. Or a pattern can be formed.

The material of the substrate usable in the present invention is not particularly limited as long as the object of the present invention is not impaired, and a glass substrate, a silicon wafer, a plastic substrate, or the like can be selected and used depending on the application. Methods for patterning the coating solution include, but are not limited to, conventional printing processes, such as inkjet printing, dip pen printing, imprinting, contact printing, roll printing, and the like. It is not. The most preferred printing method in terms of convenience and uniformity is inkjet printing or imprinting.

Patterning by the printing method using the composition of the present invention can be carried out without limitation by a conventional printing process, for example, as follows. In other words, using a Spectra Head (SE 128) and a solvent such as polyethylene glycol monomethyl ether acetate or dipropylene glycol methyl ether acetate, a coating liquid obtained by adjusting the concentration and viscosity of the metal nanoparticles to a certain range may be used as a polyimide bank (eg, For example, a width of 10 to 30 µm and a height of 1 to 2 µm) may be filled on the substrate, or CF ₄ The desired patterning may be completed by inkjet printing or imprinting on the surface of the glass substrate treated with a plasma treatment or a hydrophobic material such as a fluorine-based or siloxane-based water-repellent material. At this time, the conductivity of the film or pattern may be arbitrarily adjusted by controlling the concentration of the metal nanoparticles.

After the pattern is completed by the printing method using the coating solution, the conductive film or pattern may be formed by drying the solvent at 80 to 120 ° C., preferably at 100 ° C. for 30 seconds to 5 minutes, to further evaporate the solvent. After drying, it may be further baked at 150 to 400 ° C. for 1 to 30 minutes to form a conductive film or pattern. Upon drying, the organic material bound to the metal nanoparticles is detached and only the metal remains on the substrate to form a desired pattern.

Meanwhile, in the case of a film or a pattern made of a conductive polymer, the film or pattern has conductivity due to the movement of π electrons through a double bond in the molecular chain, so that the film or pattern is slightly green or brown in order to have sufficient conductivity. The film or pattern formed using the metal nanoparticles according to the present invention has the advantage of having high conductivity while being transparent in visible light. Accordingly, the metal nanoparticles of the present invention are subjected to blending with conductive or non-conductive polymers, as necessary, to antistatic washable sticky mats, antistatic shoes, conductive polyurethane printer rollers. (conductive polyurethane printer roller), conductive wheels and industrial rollers, antistatic pressure sensitive adhesive film, electromagnetic interference shielding, etc. have.

Hereinafter, the present invention will be described in detail with reference to Examples, but these Examples are only for illustrating the present invention and should not be construed as limiting the protection scope of the present invention.

Production Example  1: Preparation of Gold Nanoparticles

25 mL of Hydrogen perculatorate (HAuCl ₄ · H ₂ O) solution (40 mM) was added to a solution of 50 mM tetraoctylamonium bromide dissolved in 20 mL toluene and stirred. A 25 mL aqueous solution of 0.4 g of sodium borohydride (NaBH ₄ ) was added to the solution (orange), and the reaction was performed under stirring for 2 hours to obtain a dark purple solution. The reaction solution was left to stand and separated into an organic layer and an aqueous layer, and the organic layer was washed with 0.1 M sulfuric acid, 1 M sodium carbonate solution, and water, dried over MgSO ₄ , filtered with a 0.5 μm PTFE syringe filter, and then subjected to organic toluene. Dispersed. As a result of measuring the TEM, an organic solution in which gold nanoparticles having an average size of 3 to 8 nm were dispersed was obtained. The organic solution was centrifuged to obtain pure gold nanoparticles from the supernatant.

Production Example  2: Preparation of Silver Nanoparticles

A solution containing 5 g of AgNO ₃ in 0.1 liter distilled water was put in a 0.3 liter ice solution made of 2 × 10 ⁻³ M sodium borohydride (NaBH ₄ ) and stirred for 2 hours. The solution was centrifuged to separate the supernatant and the resulting slurry was dried over MgSO ₄ , poured into toluene and filtered through a 0.5 μm PTFE syringe filter. As a result of measuring the TEM, an organic solution in which silver nanoparticles having an average size of 4 to 8 nm were dispersed was obtained. The organic solution was again centrifuged to separate the supernatant to obtain pure silver nanoparticles.

Production Example  3: Preparation of Copper Nanoparticles

300 mg of copper hydrazine carboxylate (CHC) prepared from cupric chloride and hydrazine carboxylic acid (N ₂ H ₃ COOH) was dissolved in 100 mL distilled water and refluxed under nitrogen atmosphere at 80 ° C. for 3 hours. At this time, the blue solution turns red, indicating that the solution is made of metallic copper. The supernatant was separated by centrifugation of the organic solution to obtain pure copper nanoparticles. As a result of measuring the TEM, an organic solution in which copper nanoparticles having an average size of 5 to 10 nm was dispersed was obtained.

Production Example  4: Preparation of Palladium Nanoparticles

Hydrazine (N ₂ H ₄ ) (40 mM, 10 mL) was added dropwise to 100 mL of a yellow solution of Na ₂ PdCl ₄ (5 mM, 15 mL), and reacted for 3 hours to obtain a brown solution containing palladium nanoparticles. . The supernatant was separated by centrifugation of the solution to obtain pure palladium nanoparticles. As a result of measuring the TEM, palladium nanoparticles having an average size of 3 to 10 nm were obtained.

Production Example  5: Platinum  Preparation of Nanoparticles

5 mL of 0.06 M sodium borohydride (NaBH ₄ ) was mixed with 10 mL of 0.0033 M hydrogen hexachloroplatinate (IV) hexahydrate (H ₂ PtCl ₆ .6H ₂ O), stirred and reacted for 2 hours. Proceed to give a dark brown reaction solution. The dispersion was left to separate into an organic layer and an aqueous layer, and the organic layer was dried over MgSO ₄ and filtered through a 0.5 μm PTFE syringe filter. As a result of measuring TEM, platinum nanoparticles having an average size of 2 to 5 nm were obtained.

Example  1: Introduction of organic material on the surface of gold nanoparticles

0.2 g of the gold nanoparticles obtained in Preparation Example 1 was slowly stirred for 20 minutes in 50 mL of a 1: 1 solution of concentrated sulfuric acid and 30% hydrogen peroxide, diluted with 250 mL of distilled water, filtered through a 0.2 μm filter, and filtered with 5 mL of 50 mL methanol. Washed once and dried for 5 hours at 160 ℃ oven. 0.1 g of dried gold nanoparticles was added to 1.3 mL of 4-cyanophenol in 200 mL of toluene and stirred for 72 hours. The product was filtered through a 0.2 μm filter, washed twice with THF, and dried under reduced pressure in a 30 ° C. oven to obtain gold nanoparticles having hydroxyl groups linked to isocyanide groups on the surface.

Example  2: introduction of organic material on the surface of silver nanoparticles

Instead of gold nanoparticles, except that 0.2g of the silver nanoparticles obtained in Preparation Example 2 was used in the same manner as in Example 1, to obtain a silver nanoparticle having a hydroxyl group connected to the isocyanide group on the surface It was.

Example  3: introduction of organic material on the surface of copper nanoparticles

Instead of gold nanoparticles, except that 0.2g of the copper nanoparticles obtained in Preparation Example 3 was used in the same manner as in Example 1, the copper nanoparticles having a hydroxyl group connected to the isocyanide group on the surface Obtained.

Example  4: introduction of organic material on the surface of palladium nanoparticles

Except for using the gold nanoparticles, 0.2g of palladium nanoparticles obtained in Preparation Example 4, was carried out in the same manner as in Example 1 to provide a palladium nanoparticle having a hydroxyl group connected to the isocyanide group on the surface Obtained.

Example  5: Platinum  Introduction of organic material on the surface of nanoparticles

Instead of gold nanoparticles, except that 0.2g of the platinum nanoparticles obtained in Preparation Example 5 were used, the same procedure as in Example 1 was carried out to provide platinum nanoparticles having hydroxyl groups connected to isocyanide groups on the surface thereof. Obtained.

Example  6: Alkoxy on the surface of gold nanoparticles Silyl  Introduction

0.2 g of the gold nanoparticles obtained in Preparation Example 1 was slowly stirred for 20 minutes in 50 mL of a 1: 1 solution of concentrated sulfuric acid and 30% hydrogen peroxide, and then diluted with 250 mL of distilled water. Dry in oven for 5 hours. 0.1 g of dried gold nanoparticles was added to 200 mL of toluene together with 0.2 g of N- [3- (trimethoxysilyl) propylethylene diamine] and stirred for 72 hours. The product was filtered through a 0.2 μm filter, washed twice with THF, and dried under reduced pressure in an oven at 30 ° C. to obtain gold nanoparticles into which trimethoxysilyl groups were introduced.

Example  7: Pattern formation and conductivity measurement using metal nanoparticles

Inkjet composition liquids 1 to 5, each of 0.1 g of the metal nanoparticles obtained in Examples 1 to 5 and 10 g of propylene glycol methyl ether acetate (PGMEA) as a solvent, were prepared. The composition solution was sonicated for 1 hour, and each component was sufficiently mixed, filtered with a 0.5 micron syringe, printed on ink glass on a surface treated with CF ₄ Plasma, and dried at 100 ° C. for 1 minute to remain on the printing surface. Any solvent was removed. The conductive film thus formed was calcined at 250 to 400 ° C. for 1 minute to obtain a metal nanoparticle film having a desired pattern. Conductivity was measured by calculating the thickness with a 4 point probe using Jandel Universal 4 Point Probe Station, and the results are shown in Table 1.

Example  8: Pattern formation and conductivity measurement using metal nanoparticles and conductive polymers

2 to 10 g of each of the metal nanoparticles obtained in Examples 1 to 5, 0.5 g of a polythiophene (PT) 3% DMF solution as a conductive polymer, and 100 g of propylene glycol methyl ether acetate (PGMEA) as a solvent were prepared. It was. The composition solution was sonicated for 1 hour, and each component was sufficiently mixed, filtered with a 0.5 micron syringe, printed on ink glass on a surface treated with CF ₄ Plasma, and dried at 100 ° C. for 1 minute to remain on the printing surface. The solvent was removed to obtain a metal nanoparticle film with a desired pattern. Conductivity was measured by calculating the thickness with a 4 point probe, the results are shown in Table 2.

Example  9: metal nanoparticles and Non-conductive  Pattern formation and conductivity measurement using polymer

5 g each of the metal nanoparticles obtained in Examples 1 to 5, 0.1 g of polystyrene (PS) (molecular weight 5,000) as a non-conductive polymer, 50 g of propylene glycol methyl ether acetate (PGMEA) and 50 g of dipropylene glycol methyl ether acetate as a solvent. The inkjet composition liquids 11-15 which consisted of were prepared. The composition solution was sonicated for 1 hour each to sufficiently mix each component and filtered through a 0.5 micron syringe, CF ₄ After inkjet printing on the glass surface-treated with Plasma, and dried for 1 minute at 100 ℃ to remove the solvent remaining on the printing surface to obtain a metal nanoparticle film with a desired pattern. Conductivity was measured by calculating the thickness with a 4 point probe, the results are shown in Table 3.

Example  10: Pattern formation and conductivity measurement using two kinds of metal nanoparticles

Inkjet composition 16 consisting of 3 g each of the metal nanoparticles obtained in Examples 1 to 5, 1 g of the metal nanoparticles obtained in Example 6, 50 g of propylene glycol methyl ether acetate (PGMEA) and 50 g of dipropylene glycol methyl ether acetate as a solvent. To 20 were prepared. The composition solution was sonicated for 1 hour each to sufficiently mix each component and filtered through a 0.5 micron syringe, CF ₄ After printing by inkjet on the glass surface-treated with Plasma, and dried for 1 minute at 100 ℃ to remove the solvent remaining on the printing surface. The conductive film thus formed was calcined at 250 to 400 ° C. for 1 minute to obtain a metal nanoparticle film having a desired pattern. Conductivity was measured by calculating the thickness with a 4 point probe, the results are shown in Table 4.

As can be seen from the results of Tables 1 to 4, when the metal nanoparticles of the present invention are used, a pattern having a high conductivity can be obtained without undergoing etching, photolithography, or the like, and a conductive polymer or a non-conductive Even when used in combination with a polymer, it is possible to obtain a film having a predetermined level or higher conductivity. In particular, when a mixture of metal nanoparticles having an alkoxy silyl group introduced therein is used, a pattern having better conductivity can be obtained.

As described in detail above, in the case of the metal nanoparticles according to the present invention, a conductive film or a pattern can be easily formed by a printing method, the obtained film or conductivity is very excellent, and the conductivity can be arbitrarily adjusted as necessary. It can be advantageously used for antistatic adhesive sheets or shoes, conductive polyurethane print rollers, electromagnetic interference shielding (Electromagnetic Interference Shielding).

Claims (17)

Metal nanoparticles having a magnetic molecule assembly layer formed of a compound of formula 1 on the surface: [Formula 1] X-Y Where X is NC, NH ₂ , COOH, or phosphate, Y is a monovalent organic group having 1 to 30 carbon atoms or OH, NH ₂ , NO ₂ , methoxy, ethoxy, phenoxy, halogen atom, hetero sulfur group, hetero amine, oxadiazole, triphenylamine copper phthalocyanine and carba It is a C1-C30 polyvalent organic group which has one or more substituents chosen from the group which consists of a sol. Metal nanoparticles formed with a magnetic molecular assembly layer consisting of a compound of formula 2 on the surface: [Formula 2] X-Z Where X is SH, NC, NH ₂ , COOH, or phosphate, Z is-(CH ₂ ) _n -Si (OR) R ₁ R ₂ , wherein R ₁ and R ₂ are each independently CH ₃ or OR, R is an alkyl group having 1 to 20 carbon atoms, and n is 1 to Is an integer of 10. The method of claim 1, The metal nanoparticles are metal nanoparticles of gold, silver, copper, palladium, or platinum having a diameter of 1 to several hundred nm, Y in Formula 1 is -CONH-, -COO-, -CO-, -CH _2- , -Si-, bis- (porphyrin) [bis- (porphyrin)],

,

And

Metal nanoparticles, characterized in that the monovalent or divalent organic group having 1 to 30 carbon atoms that may include one or more selected from the group consisting of. The method of claim 2, The metal nanoparticles are metal nanoparticles of gold, silver, copper, palladium, or platinum having a diameter of 1 to several hundred nm, Z in Formula 2 is-(CH ₂ ) _n -S _i (OR) ₃ or-(CH ₂ ) _n -Si (OR) (CH ₃ ) ₂ (wherein R is an alkyl group having 1 to 10 carbon atoms, n is an integer of 1 to 6). According to claim 1, wherein the compound of formula 1 is butyl isocyanide (butyl isocyanide), tert-butyl isocyanide (tert-butyl isocyanide), 1,1,3,3-tetramethylbutyl isocyanide ( 1,1,3,3-tetramethylbutyl isocyanide), 1,6-diisocyanohexane, cyclohexyl isocyanide, cyanomethyl N, N-dimethyldithiocarba Cyanomethyl N, N-dimethyldithiocarbamate, 1-cyano-N-methylthioformamide, benzyl cyanide, 2-naphthylacetonitrile ), 4-phenylbutyronitrile, 3-anilinopropionitirle, 3- (benzylamino) propionitrile, 3-methylbenzyl cya 2-methylbenzyl cyanide, 2-fluorophenylacetonitrile, 2-chlorobenzyl cyanide nzyl cyanide), 2-bromophenylacetonitrile, 3-chlorobenzylcyanide, (3-methoxyphenyl) -acetonitrile, (3-methoxyphenyl) acetonitrile, 3 3-phenoxyphenylacetonitrile, 1,3-phenylenediacetonitrile, 4-hydroxybenzyl cyanide, 4-methoxyphenyl Acetonitrile (4-methoxyphenyl) actonitrile, 4-aminobenzyl cyanide, 4-nitrophenylacetonitrile, 4'-chloro-2-cyanoacetanilide (4 ') -chloro-2-cyanoacetanilide, 4-cyanophenol, 4-biphenylcarbonitrile, 4'pentyl-4-biphenylcarbonitrile , 4'-hexyl-4-biphenylcarbonitrile, 4'-hydroxy-4-biphenylcarbonitrile, 9-anthracene carbon Isocyanatomethyl cyanide based compound comprising a casting reel (9-anthracenecarbonitrile); Aniline, 4-ethylaniline, 4-cyclohexylaniline, 4-cyclohexylaniline, 2,3-diaminophenol, 3,4-difluoroaniline 3,4-difluoroaniline, 4-aminobiphenyl, 9-aminophenanthrene, 1-aminoindan, 3,5-dimethoxybenzylamine (3, 5-dimethoxybenzylamine), 3,4,5-trimethoxybenzylamine, 1,9-diaminononane, 1,10-diaminodecane (3,4,5-trimethoxybenzylamine) Amine compounds including 1,10-diaminononane), 1,12-diaminonododecane, tetraethylenepentamine, and 1-adamantaneamine; Octanoic acid, undecanoic acid, undecadioic acid, ethoxyacetic acid, cycloheptane carboxylic acid, 1-adamant Tanacetic acid (1-adamantaneacetic acid), phenylacetic acid (phenylacetic acid), 6-phenylhexanoic acid (6-phenylhexanoic acid), 4-fluorophenylacetic acid (4-fluorophenylacetic acid), 4-hydride 4-hydroxycinnamic acid, salicylic acid, 4-tert-butylbenzoic acid, 1,3,5-benzenetricarboxylic acid (1, 3,5-benzenetricarboxylic acid), 2,5-dinitrobenzoic acid, 3,5-di-tert-butylbenzoic acid (3,5-di-tert-butylbenzoic acid ), Gallic acid, 4,4'-biphenyldicarboxylic acid, 1-naphtholic acid (1-naphtholic acid), 9-fluorene 9-fluorenecarboxylic acid, 1-pyrenecarboxylic acid, carbobenzooxyglycine, 6- (carbenzyloxyamino) -caproic acid [6- (carbobenzyloxyamino) a carboxylate compound including -caproic acid]; And diphenyl phosphite, dibenzyl phosphite, bis (4-nitrobenzyl) phosphate [Bis (4-nitrobenzyl) phosphite], dimethyl (3-phenoxyacetonyl) phosphate [dimethyl ( (3-phenoxyacetonyl) phosphate], triphenyl phosphite, benzyl diethyl phosphite, phenyl phosphinic acid, ethyl phenyl phosphate, bis (4 Methoxyphenyl) phosphonic acid, dimethyl phenylphosphonite, diethyl phenylphosphonite, diphenyl phosphonic acid, diphenyl phosphonic acid, phenyl phosphonic acid acid), (4-aminobenzyl) phosphonic acid [(4-aminobenzyl) phosphonic acid], diphenyl methyl phosphate, 1-naphthyl phosphate, 1,1'-bi Naphthyl-2,2'-dil hydrogen phosphate Metal nanoparticles, characterized in that selected from the group consisting of phosphate-based compounds comprising (1,1'-binaphthyl-2,2'-diyl hydrogen phosphate). According to claim 1, wherein the compound of formula 2 is N- [3- (trimethoxysilyl) propylethylene diamine] [N- (3- (trimethoxysilyl) propylethylene diamine], 3-aminopropylmethyldimethoxysilane (3 -aminopropylmethyldimethoxysilane, mercaptomethylmethyldiethoxysilane, m-aminophenyltrimethoxysilane, 4-aminobutyltriethoxysilane, N- (2-aminoethyl ) -3-aminopropylmethyldimethoxysilane [N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane], 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane (3 -mercaptopropylmethyldimethoxysilane) 3-mercaptopropyltriethoxysilane, 4- (triethoxysilyl) butyronitrile [4- (triethoxysilyl) butyronitrile] and 3- (triethoxysilyl) propylthioisocyanate [ 3- (triethoxysilyl) propylthiocyanate] Metal nanoparticles being selected from the group consisting of. A metal nanoparticle composition comprising a metal nanoparticle according to claim 1 and a metal nanoparticle according to claim 2. The metal nanoparticle composition of claim 7, wherein the metal nanoparticles of claim 1 and the metal nanoparticles of claim 2 comprise 1: 1 to 10: 1. 9. At least one metal nanoparticle among the metal nanoparticles according to claim 1 or the metal nanoparticles according to claim 2; And a pattern forming composition comprising an organic solvent. The pattern forming composition of claim 9, wherein the metal nanoparticle comprises 0.01 to 80 wt%. The pattern forming composition of claim 9, further comprising at least one polymer of a conductive or nonconductive polymer in the composition. The method of claim 11, wherein the conductive polymer is polyacetylene (PA), polythiophene (PT), poly (3-alkyl) thiophene (poly (3-alkyl) thiophene: P3AT), polypyrrole : PPY), polyisothianapthelene (PITN), polyethylene dioxythiophene (PEDOT), polyparaphenylene vinylene (PPV), poly (2,5-dialkoxy) paraphenylene vinyl [Poly (2,5-dialkoxy) paraphenylene vinylene], polyparaphenylene [polyparaphenylene (PPP), polyparaphenylene sulphide (PPS), polyheptadiyne (PHT), poly (3-hexyl Theophene is one or more selected from the group consisting of [poly (3-hexyl) thiophene: P3HT], and polyaniline [polyaniline: PANI], and is contained in a proportion of 1 to 15 parts by weight per 100 parts by weight of the metal nanoparticles. Pattern forming composition, characterized in that. The method of claim 11, wherein the non-conductive polymer is polyester, polycarbonate, polyvinyl alcohol, polyvinyl butyral, polyacetal, polyarylate, polyamide, polyamideimide, polyetherimide, polyphenylene ether, poly Phenylene sulfide, polyether sulfone, polyether ketone, polyphthalamide, polyether nitrile, polyether sulfone, polybenzimidazole, polycarbodiimide, polysiloxane, polymethyl methacrylate, polymethacrylamide, nitrile rubber, Acrylic rubber, polyethylene tetrafluoride, epoxy resin, phenol resin, melamine resin, urea resin, polybutene, polypentene, ethylene-propylene copolymer, ethylene-butene-diene copolymer, polybutadiene, polyisoprene, ethylene-propylene- Diene copolymer, butyl rubber, polymethylpentene, polystyrene, styrene-butadiene copolymer, hydrogenated ( hydrogenated) is one or more selected from the group consisting of styrene-butadiene copolymer, hydrogenated polyisoprene, and hydrogenated polybutadiene, for pattern formation, characterized in that it comprises 0.1 to 10 parts by weight per 100 parts by weight of the metal nanoparticles Composition. Iii) printing and patterning the composition according to any one of claims 9 to 13 on a substrate; And ii) drying the conductive pattern. The method of claim 14, wherein the printing method is inkjet printing, dip pen printing, imprinting, contact printing, or roll printing. The method of claim 14, further comprising firing after the step ii). The method of claim 16, wherein the firing is performed at 150 to 400 ° C. for 1 minute to 30 minutes.

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