WO2011013542A1 - Metal nanoparticles, dispersion containing same, and process for production of same - Google Patents
Metal nanoparticles, dispersion containing same, and process for production of same Download PDFInfo
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- WO2011013542A1 WO2011013542A1 PCT/JP2010/062200 JP2010062200W WO2011013542A1 WO 2011013542 A1 WO2011013542 A1 WO 2011013542A1 JP 2010062200 W JP2010062200 W JP 2010062200W WO 2011013542 A1 WO2011013542 A1 WO 2011013542A1
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/20—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds
- B22F9/22—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds using gaseous reductors
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/30—Making metallic powder or suspensions thereof using chemical processes with decomposition of metal compounds, e.g. by pyrolysis
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/52—Electrically conductive inks
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
Definitions
- the present invention relates to metal nanoparticles (meaning nanometer-size metal fine particles), metal compound nanoparticles (meaning nanometer-size metal compound fine particles), and a method for producing a dispersion thereof.
- metal nanoparticles and metal compound nanoparticles are collectively referred to as “metal nanoparticles”.
- the aggregation-inhibiting substance and this reduction reaction product are usually composed of organic substances that do not have electrical conductivity, the dispersion of metal nanoparticles obtained by the chemical reduction method is applied to conductive coatings, etc.
- a step of removing the organic substance and its reduction reaction product (in some cases, a reduction reaction byproduct containing an unreacted reducing agent) to develop conductivity is indispensable.
- a method for producing silver nanoparticles is known in which dispersibility is maintained by adsorbing organic substances such as citric acid on the surface of silver nanoparticles.
- organic substances such as citric acid
- the silver nanoparticles obtained by this method have lost their conductivity due to the adsorption of organic matter, regardless of the silver nanoparticles that should have high conductivity.
- the obtained silver nanoparticles are applied to a conductive coating film or the like, not only must it be heated at 150 ° C. or higher in order to remove organic substances, but even if it has conductivity, it has extremely high surface resistance. Only a coating film with a large electrical property was obtained.
- the present invention has a technical problem to provide a method for producing a large amount of metal-based nanoparticles that are stably dispersed in a solvent without containing an organic substance such as an aggregation inhibitor and a reducing agent at a low cost.
- the present inventor has found that the above object can be achieved by a simple method, and has completed the present invention. That is, the present invention relates to metal-based nanoparticles, a dispersion containing the same, and a method for producing the same.
- the metal-based nanoparticle dispersion according to the present invention is obtained by suspending a powder of a metal compound (in the present invention, this is sometimes referred to as “raw material powder”) in a solvent, and the suspension is non-oxidized. It is obtained by heating in a reactive gas atmosphere and is characterized in that high dispersion stability can be maintained without containing an aggregation-inhibiting substance such as a surfactant.
- the metal-based nanoparticles of the present invention can be obtained as a dispersion by suspending the raw material powder in a solvent and heating the suspension in a non-oxidizing gas atmosphere.
- the dispersion does not need to contain an aggregation inhibitor for inhibiting aggregation of the metal-based nanoparticles.
- the non-oxidizing gas referred to in the present invention means an inert gas such as nitrogen or argon or a reducing gas such as hydrogen gas.
- the non-oxidizing gas is bubbled into the raw material powder suspension in the container while the material powder suspension is in the container.
- the raw material powder suspension is oxidative gas such as air, oxygen, etc.
- metal-based nanoparticles obtained by reducing the raw material metal compound powder can be produced.
- silver nanoparticles can be obtained by using silver oxide (Ag 2 O) powder as raw material powder
- copper oxide (I) can be obtained by using copper hydroxide [Cu (OH) 2 ] powder as raw material powder.
- metal-based nanoparticles of the present invention if metal nanoparticles of the same metal type as the raw material powder are mixed in advance as a seed particle in the suspension composed of the raw material powder and the solvent, the premixed metal Metal nanoparticles of the same type and size as the system nanoparticles can be efficiently produced.
- the metal-based nanoparticle dispersion liquid of the present invention is characterized in that the dispersion state can be stably maintained over a long period of time in a relatively uniform state with a maximum particle diameter of 50 nm, although it does not contain an aggregation inhibitor. It is.
- the metal compound powder (raw material powder) as a raw material is “reductive substance conversion” at a predetermined heating temperature in a solvent in an environment of a non-oxidizing gas such as an inert gas or hydrogen gas.
- a non-oxidizing gas such as an inert gas or hydrogen gas.
- Any kind of metal may be used as long as (details will be described later) occurs.
- the metal-based nanoparticles in the metal-based nanoparticle dispersion of the present invention have a particle size of 50 nm or less, the particle size distribution is substantially Gaussian, and have a single crystal facet on at least a part of the particle surface, that is, a crystal It is characterized by extremely high properties. However, it is not necessary for all the particles to be a complete single crystal.
- the solvent used in the present invention is preferably ⁇ -butyrolactone, diacetone alcohol, cyclohexanone or other ketones or carbonyl compounds having a boiling point of 100 ° C. or higher, or tetradecane or other high boiling alkanes having a boiling point of 100 ° C. or higher.
- the metal-based nanoparticle dispersion according to the present invention can be suitably used as a main component of, for example, a conductor forming ink.
- the ink for forming a conductor according to the present invention can be suitably used as a film forming method for forming a conductor by an inkjet method, a spin coating method, a relief printing method, an intaglio printing method, or a screen printing method. .
- the metal-based nanoparticles according to the present invention can be produced in large quantities and at low cost by a simple operation and equipment that only heats a suspension of raw material powder in a non-oxidizing atmosphere.
- the metal-based nanoparticles obtained in this way are skillfully limited in their particle size by a mechanism closely related to the autocatalytic growth function in the production process, and in a solvent, a dispersant or a surfactant. High dispersion stability is maintained without adding a coagulation inhibitor such as the above. That is, there is no strong organic protective film on the surface of the metal-based nanoparticles according to the present invention except for the adsorption of the solvent.
- the metal-based nanoparticles according to the present invention are expected to have a wide range of applications including conductor forming inks.
- Example 1 it is a series of absorption spectra measured at the end of each step of the silver nanoparticle dispersion obtained when a total of eight steps are repeated.
- B An example of a TEM image showing the presence of triangular single-crystal facets, observed at higher magnification.
- Example 1 Even when the solvent of the silver nanoparticle dispersion obtained in Example 1 was forcibly evaporated and a high-concentration silver nanoparticle dispersion having a concentration of about 25% by mass was prepared with this, the silver nanoparticle was a surfactant or the like. It is an absorption spectrum showing that high dispersion stability is maintained without addition. It is a series of spectra of the silver nanoparticle dispersion liquid obtained in Example 2 using a larger silver oxide powder as a raw material powder under the same conditions as in Example 1. (A) is the silver obtained in Example 3 in which silver nanoparticles were prepared under the same conditions as in Example 1 using silver nanoparticles previously prepared by the laser method described in Non-Patent Document 1 as seed particles.
- Example 2 is a series of spectra of a nanoparticle dispersion.
- B is a series of spectra obtained in a similar experiment when the seed particles are laser-annealed, and shows that a large difference occurs in the autocatalytic growth function depending on the presence or absence of annealing.
- It is a series of absorption spectra of the nanoparticle dispersion liquid in Example 4 in which copper (I) oxide nanoparticles were prepared using copper hydroxide powder as a raw material in a non-oxidizing atmosphere under an environment of hydrogen gas. Under the same conditions as in the experiment of FIG.
- Example 7 copper oxide nanoparticles prepared in advance by a laser method were used as seed particles, and copper (I) (Cu 2 O) nanoparticles having a small particle diameter were prepared by autocatalytic growth. It is a series of absorption spectra of the nanoparticle dispersion liquid in Example 5. It is a series of absorption spectra of the nanoparticle dispersion liquid in Comparative Example 2, which was carried out under the same conditions as in Example 1 and only with stirring and without bubbling of inert gas.
- metal-based nanoparticles having an autocatalytic function metal-based nanoparticles (seed particles, seeds) prepared in advance by any other method instead of the metal-based nanoparticles generated in a small amount in the first step described above. ) Can also be used, which can further increase the production efficiency of the metal-based nanoparticles.
- the mechanism by which the metal-based nanoparticles have an autocatalytic growth function is not clear, but when the metal-based nanoparticles are in contact with the raw material powder in the suspension, the metal-based nanoparticles are localized in the raw material powder. It is inferred that new metal-based nanoparticles are generated from this part due to the function of promoting reductive substance conversion.
- the metal-based nanoparticles are reduced and generated from the raw material powder, the original metal-based nanoparticles are subjected to surface oxidation, but this is rather undesirable for the nanoparticles, which is “increase in particle size”. Not only is growth suppressed, but dispersion stability is improved.
- the method of the present invention basically includes Suspending the powder of the S1 metal compound in a predetermined solvent; S2
- the suspension is composed of two simple steps of heating the suspension at a predetermined temperature in an atmosphere of an inert gas or hydrogen gas (preferably through an inert gas or hydrogen gas).
- an inert gas or hydrogen gas preferably through an inert gas or hydrogen gas.
- the metal-based nanoparticles of the present invention are produced by reductive material conversion of a metal compound as a raw material in a solvent heated to a predetermined temperature.
- the metal nanoparticles produced can be obtained in a state of being dispersed in a solvent.
- the metal nanoparticles dispersed in a dispersion solvent different from the solvent at the time of production can be adjusted. You can also.
- the metal-based nanoparticle dispersion of the present invention can be made into a high-concentration dispersion arbitrarily exceeding the concentration at the time of production by concentration by evaporation of the solvent.
- the metal-based nanoparticles of the present invention have the greatest feature in the production process, and the generated metal-based nanoparticles promote the subsequent generation of the metal-based nanoparticles in an autocatalytic manner, thereby proliferating the metal-based nanoparticles.
- the characteristics of the metal-based nanoparticles thus obtained are determined according to various conditions such as the type of metal compound used as a raw material, its shape and size, the type of solvent, the heating temperature, the treatment time, and the type of gas that provides a non-oxidizing atmosphere. It is controlled by selecting.
- the metal compound used as the raw material is preferably an oxide or a hydroxide.
- the conditions required for the raw material must be such that significant reductive material conversion occurs at a predetermined heating temperature in a solvent in an inert gas or hydrogen gas environment. Any metal can be used as long as this condition is satisfied.
- silver oxide (Ag 2 O) is preferable for the production of silver nanoparticles, and copper (I) (Cu 2 O) or copper oxide (II) (CuO) for the production of copper or copper oxide nanoparticles.
- tin (IV) (SnO 2 ) or tin (II) oxide (SnO) can be used to produce tin nanoparticles.
- the form of the metal compound used as a raw material is preferably a powder in order to ensure effective contact with metal-based nanoparticles in a solvent. This is why the term “raw powder” is used.
- the particle size of the powder is not necessarily small, and it is necessary to select it appropriately according to the type so that the autocatalytic growth reaction proceeds efficiently.
- the solvent serves not only as a dispersion solvent for the raw material metal compound, but also for controlling the reaction in the heating step, and for stably dispersing the generated metal-based nanoparticles without adding a surfactant, Of particular importance.
- this heating step requires a temperature of 100 ° C. or higher as an experimental value. For this reason, it is desirable that the boiling point of the solvent be as high as possible.
- the dispersed metal-based nanoparticles are used after being applied and dried, an excessively high boiling point is not preferable in order to promote the volatilization of the solvent. From these viewpoints, the most preferable solvent overall is ⁇ -butyrolactone (boiling point 203 ° C.).
- ketones carbonyl compounds
- diacetone alcohol boiling point 168 ° C.
- cyclohexanone boiling point 156 ° C.
- high-boiling alkanes having a boiling point exceeding 100 ° C. such as tetradecane
- the metal-based nanoparticles and the metal-based nanoparticle dispersion of the present invention are produced as follows.
- a metal compound powder (raw material powder) as a raw material is dispersed in the solvent, for example, ⁇ -butyrolactone.
- a typical dispersion amount is about 10 mg per mL of the solvent.
- the amount of the metal-based nanoparticles generated in the first heating step hardly increases or may decrease even if the raw material is excessively dispersed, so that an appropriate amount needs to be selected.
- an inert gas or hydrogen gas is constantly introduced by bubbling or the like.
- the amount is sufficient as long as it can prevent oxygen from being mixed.
- the solvent in which the raw material powder is dispersed is heated at a predetermined temperature until the formation reaction of the metal-based nanoparticles is completed (saturated) (typically, the time is about 30 minutes).
- the reaction residue (which has a stoichiometric composition different from that of the raw material powder), which no longer generates nanoparticles even if the process is continued, is removed by centrifugation.
- the second and subsequent steps are followed by autocatalytic activity of the existing metal nanoparticles.
- the proliferation function the yield of the metal-based nanoparticles is remarkably improved, and a metal-based nanoparticle dispersion liquid having a necessary concentration can be easily obtained.
- it is not always necessary to include an operation of centrifugation in each step and the raw material powder may be added successively and heated, and finally the sedimented component may be removed by centrifugation.
- the above steps can be repeated until the target concentration is achieved, but the target concentration can also be obtained by concentrating the dispersion by forced evaporation of the solvent at an appropriate stage.
- Example 1- Silver oxide fine powder manufactured by Fukuda Metal Foil Powder Co., Ltd. was used as the raw material powder, and ⁇ -butyrolactone special grade reagent manufactured by Wako Pure Chemical Industries, Ltd. was used as the solvent. Put 5 mL of solvent in a glass container with an internal volume of 10 mL, add about 40 mg of raw material powder to it, and stir with a magnetic stirrer and degassing conditions with about 20 mL of nitrogen gas bubbling per minute. The plate was heated at about 135 ° C. for 15 minutes.
- the precipitate is removed by centrifugation, and the state of the obtained silver nanoparticle dispersion liquid is diluted with a part of it, and a multi-layer manufactured by Hamamatsu Photonics Co., Ltd. is mainly used. Analysis was performed by absorption spectroscopy using a channel analyzer (PMA11). Thereafter, the raw material powder was added again to the dispersion, and the same process was repeated a total of 8 times. However, only the final 8th time, the raw material powder was increased about twice, and the input amount was 70 mg.
- FIG. 1 is a series of absorption spectra showing how the concentration of silver nanoparticles increased in each step in the above steps. In the vicinity of a wavelength of 400 nm, sharp absorption derived from the surface plasmon of silver nanoparticles is observed. The shape of the absorption band does not change even when the concentration of nanoparticles increases with repeated processes, and the peak position and light scattering by the dispersion are hardly seen (the transparency is very high). It can be seen that silver nanoparticles having a diameter of 30 nm or less exist predominantly in the dispersion.
- FIG. 2 is a series of TEM data that further supports the above facts.
- FIG. 2 (a) shows an example of a relatively low magnification TEM image showing the degree of particle size distribution in silver nanoparticles
- FIG. 2 (b) shows the particle size distribution obtained based on these.
- FIG. 3 (a) and 3 (b) show TEM images with higher magnification than FIG. 2 (a).
- FIG. 3C shows an electron diffraction spot image.
- the concentration of the silver nanoparticle dispersion obtained after the final eighth step shown in FIG. 1 is more than 1% by mass.
- the concentration can be adjusted to an arbitrary concentration according to, for example, printing characteristics of a target film forming method, and can be up to 20% by mass or more. Further increase is desirable. This higher concentration can be achieved by further repeating the above steps, but here, as a simpler method, concentration by forced evaporation of the solvent was attempted.
- FIG. 4 is an absorption spectrum of the dispersion liquid whose concentration is increased to about 25% by mass by this method. Despite such a high concentration, a sharp plasmon absorption band was still maintained, and formation of coarse nanoparticles that caused light scattering was not observed. This indicates that the silver nanoparticles of this example have been demonstrated to maintain very high dispersibility in a solvent without the addition of a surfactant or the like.
- Example 2- Silver oxide fine powder manufactured by Wako Pure Chemical Industries, Ltd. was used as the raw material powder under the same conditions as in Example 1. Compared to the raw material powder used in Example 1, there is a difference that the particle size is large.
- FIG. 5 is a spectrum corresponding to FIG. 1 when a total of seven steps are repeated using about 40 mg of raw material powder per step. However, in the final seventh step, the amount of raw material powder was 200 mg. The silver nanoparticles produced in the first to third steps were rather improved as compared with Example 1. On the other hand, in the subsequent steps, the silver nanoparticles per step was about 5 mg, which was lower than in the case of Example 1, and the conversion rate from the raw material to silver nanoparticles was only about 10%.
- Example 3- In order to examine the presence or absence of the autocatalytic growth function of silver nanoparticles prepared in advance by another method, silver nanoparticles prepared using the laser method described in Non-Patent Document 1 were used. The conditions are the same as in Example 1 except that the arbitrary amount is added as seed particles together with the raw material powder in the first step. However, the process was repeated a total of four times.
- FIG. 6A shows a series of absorption spectra obtained at this time. Unlike FIG.1 and FIG.4, the quantity of the silver nanoparticle obtained by one process decreased rather as the number of processes increased. At the same time, it can be seen that the peak position of the spectrum is gradually shifted to the longer wavelength side.
- silver nanoparticles prepared by the same laser method as described above are further irradiated with laser light having a wavelength of 1064 nm, and a kind of laser annealing (the silver nanoparticles are heated by pulse laser irradiation to improve the crystallinity of the particles).
- the number of seed particles can be obtained in one step with an increase in the number of steps, although the amount of seed particles is greatly reduced.
- the amount of silver nanoparticles obtained increased steadily as in Example 1. There is no change in the peak position of the spectrum. That is, the seed particles used here have an autocatalytic growth function.
- FIG. 6 (a) and FIG. 6 (b) suggests that the high crystallinity of the nanoparticles plays an important role in the expression of the autocatalytic growth function.
- Example 4- A copper hydroxide powder manufactured by Wako Pure Chemical Industries, Ltd. was used as a raw material powder, and a ⁇ -butyrolactone special grade reagent manufactured by Wako Pure Chemical Industries, Ltd. was used as a solvent.
- a ⁇ -butyrolactone special grade reagent manufactured by Wako Pure Chemical Industries, Ltd. was used as a solvent.
- Into a glass container with an internal volume of 10 mL 5 mL of solvent is added, and about 60 mg of copper hydroxide is added thereto. Under stirring conditions with a magnetic stirrer and degassing conditions with about 20 mL of nitrogen gas bubbling per minute, Using a hot plate, it was heated at 170-180 ° C., which is close to the boiling point of ⁇ -butyrolactone, for 20 minutes. After cooling to near room temperature, the sediment was removed by centrifugation, and the state of the dispersion was analyzed by absorption spectroscopy.
- FIG. 7 is a series of spectra of a copper (I) oxide (Cu 2 O) nanoparticle dispersion produced in the above process while divalent copper is reduced to monovalent copper in a nitrogen atmosphere.
- the weight of the Cu 2 O nanoparticles produced in the first step is less than 1 mg, which is about 1% of the input raw material powder of 60 mg.
- the maximum weight obtained is 44 mg.
- the spectrum of FIG. 7 has a large tail on the long wavelength side, and the dispersion exhibits relatively strong light scattering.
- the size of the nanoparticles is relatively large and includes particles having a diameter of 50 nm or more. It is estimated that The same applies to the nanoparticles produced after the second step, but the amount produced per step increased to nearly four times that of the first step in the second to seventh steps. Again, a significant autocatalytic growth function is expressed here.
- Example 5 Under the same conditions as in Example 4, copper (I) oxide nanoparticles obtained by oxidizing copper nanoparticles previously prepared by a laser method were used as seed particles. As shown in FIG. 8, the results more clearly show the essential role of the autocatalytic growth function that characterizes the present invention. That is, in FIG. 8, the spectrum of the seed particles used in this example shows a relatively sharp rise from the vicinity of 500 nm toward the short wavelength side, and the absorption on the long wavelength side is small. This represents the nature of small copper (I) oxide nanoparticles with a particle size of 10 nm. Furthermore, it can be read from the spectrum of FIG. 8 that nanoparticles produced with much higher efficiency after the second step also have similar properties. The difference in the experimental conditions of FIG.
- FIG. 7 for Example 4 and FIG. 8 for the present example is only the difference in seed particles. Nevertheless, such a large difference appears in the nanoparticles generated in the repetition process, as if the seed particles had some kind of genetic information. It supports a mechanism closely related to the autocatalytic growth function that grows in the process.
- Example 1 from the solvent heated to a temperature of 130 ° C. or higher, dissolved oxygen is also removed from the system as the solvent evaporates. In the first and second steps, a non-oxidizing atmosphere is used. However, as the generation of silver nanoparticles, oxygen is constantly released from the raw material powder and gradually accumulates in the system.
- the metal-based nanoparticles according to the present invention are based on a specific action of an autocatalytic growth function, a container for dispersing a raw metal compound powder in a solvent selected as appropriate, and a gas supply that provides a non-oxidizing atmosphere,
- a gas supply that provides a non-oxidizing atmosphere
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Abstract
Description
なお、界面活性剤、クエン酸などのように金属系ナノ粒子の凝集防止の目的に使用される物質を、本明細書においては、「凝集抑制物質」とよぶ。そして、凝集抑制物質やこの還元反応生成物は通常、いずれも導電性を有しない有機物で構成されるため、化学還元法で得られる金属系ナノ粒子の分散液を導電性の塗膜などに適用する場合、有機物やその還元反応生成物(場合によっては未反応の還元剤を含む還元反応副生成物)を除去して導電性を発現させる工程が必要不可欠であった。 In the chemical reduction method, in order to avoid aggregation of the metal-based nanoparticles, it is necessary to coat the surface of the metal-based fine particles with a large amount of an organic protective film using a surfactant, citric acid, or the like. In addition, a large amount of reducing agent is required to prepare a high-concentration metal-based nanoparticle dispersion.
In addition, a substance used for the purpose of preventing aggregation of metal-based nanoparticles, such as a surfactant and citric acid, is referred to as “aggregation suppressing substance” in this specification. In addition, since the aggregation-inhibiting substance and this reduction reaction product are usually composed of organic substances that do not have electrical conductivity, the dispersion of metal nanoparticles obtained by the chemical reduction method is applied to conductive coatings, etc. In this case, a step of removing the organic substance and its reduction reaction product (in some cases, a reduction reaction byproduct containing an unreacted reducing agent) to develop conductivity is indispensable.
本発明にいう、非酸化性ガスとは、窒素、アルゴンなどの不活性ガス又は水素ガスなどの還元性のガスを意味する。
原料粉懸濁液を非酸化性ガス雰囲気下で加熱するには、容器内の原料粉懸濁液内に非酸化性ガスを通気(バブリング)しながら、原料粉懸濁液の入った容器内に非酸化性ガスを通気しながら、又は、非酸化性ガスと原料粉懸濁液とを容器に充填して加熱するなどの方法により、原料粉懸濁液が空気、酸素などの酸化性気体に接しない条件下で加熱する。そしてこの加熱は、懸濁液を攪拌、振とうなどの方法により原料粉の懸濁状態を保持しながら実施される。
加熱温度は、通常、100℃~溶媒の沸点の範囲である。
本発明の方法によって、原料の金属化合物粉末(原料粉)が還元された金属系ナノ粒子を製造することができる。
例えば、酸化銀(Ag2O)粉末を原料粉として使用することにより銀ナノ粒子を得ることができ、水酸化銅[Cu(OH)2]粉末を原料粉として使用することにより酸化銅(I)(Cu2O)ナノ粒子を得ることができる。
本発明の金属系ナノ粒子の製造方法において、原料粉と溶媒からなる懸濁液に、原料粉と同じ金属種の金属系ナノ粒子を種粒子としてあらかじめ混入させておくと、あらかじめ混入させた金属系ナノ粒子と同種・同サイズの金属系ナノ粒子を、効率よく製造することができる。
本発明の金属系ナノ粒子分散液は、凝集抑制物質を含まないにもかかわらず、最大粒子径が50nmで比較的揃った状態で長期間に亘り、安定的に分散状態を維持できる点が特徴である。 The metal-based nanoparticles of the present invention can be obtained as a dispersion by suspending the raw material powder in a solvent and heating the suspension in a non-oxidizing gas atmosphere. The dispersion does not need to contain an aggregation inhibitor for inhibiting aggregation of the metal-based nanoparticles.
The non-oxidizing gas referred to in the present invention means an inert gas such as nitrogen or argon or a reducing gas such as hydrogen gas.
In order to heat the raw material powder suspension in a non-oxidizing gas atmosphere, the non-oxidizing gas is bubbled into the raw material powder suspension in the container while the material powder suspension is in the container. The raw material powder suspension is oxidative gas such as air, oxygen, etc. by aerating the non-oxidizing gas through the container or by filling the container with the nonoxidizing gas and the raw material powder suspension and heating. Heat under conditions not in contact with This heating is performed while maintaining the suspension state of the raw material powder by a method such as stirring and shaking the suspension.
The heating temperature is usually in the range of 100 ° C. to the boiling point of the solvent.
By the method of the present invention, metal-based nanoparticles obtained by reducing the raw material metal compound powder (raw material powder) can be produced.
For example, silver nanoparticles can be obtained by using silver oxide (Ag 2 O) powder as raw material powder, and copper oxide (I) can be obtained by using copper hydroxide [Cu (OH) 2 ] powder as raw material powder. ) (Cu 2 O) nanoparticles can be obtained.
In the method for producing metal-based nanoparticles of the present invention, if metal nanoparticles of the same metal type as the raw material powder are mixed in advance as a seed particle in the suspension composed of the raw material powder and the solvent, the premixed metal Metal nanoparticles of the same type and size as the system nanoparticles can be efficiently produced.
The metal-based nanoparticle dispersion liquid of the present invention is characterized in that the dispersion state can be stably maintained over a long period of time in a relatively uniform state with a maximum particle diameter of 50 nm, although it does not contain an aggregation inhibitor. It is.
またこのようにして得られた金属系ナノ粒子は、製造過程における自己触媒的増殖機能と密接に関連する機構により、その粒子サイズが巧妙に制限され、かつ溶媒中で、分散剤或いは界面活性剤等の凝集抑制物質を添加することなく、高い分散安定性を保持する。すなわち、本発明に係る金属系ナノ粒子の表面には、溶媒の吸着を除いて、強固な有機保護膜が存在しない。更に、主な反応副生物は水、酸素、二酸化炭素などのように、加熱工程で自動的に揮発除去されるため、これらの除去のための余分な圧力や熱の処理が不要である。このため本発明に係る金属系ナノ粒子は、導体形成用インクをはじめとする幅広い応用が期待される。 The metal-based nanoparticles according to the present invention can be produced in large quantities and at low cost by a simple operation and equipment that only heats a suspension of raw material powder in a non-oxidizing atmosphere.
In addition, the metal-based nanoparticles obtained in this way are skillfully limited in their particle size by a mechanism closely related to the autocatalytic growth function in the production process, and in a solvent, a dispersant or a surfactant. High dispersion stability is maintained without adding a coagulation inhibitor such as the above. That is, there is no strong organic protective film on the surface of the metal-based nanoparticles according to the present invention except for the adsorption of the solvent. Further, since main reaction by-products are automatically removed by volatilization in the heating process, such as water, oxygen, carbon dioxide, etc., no extra pressure or heat treatment is required for the removal. Therefore, the metal-based nanoparticles according to the present invention are expected to have a wide range of applications including conductor forming inks.
(金属系ナノ粒子生成の手順)
金属酸化物からなる原料粉を、溶媒中、非酸化性雰囲気で所定の温度で加熱すると、原料粉の大半は未変化もしくは酸素比率が有意に低下した金属酸化物粉に変換されるだけであるが、同時に少量の金属系ナノ粒子(割合にして1%~数%(質量パーセント))が生成される。
このようにして生成した少量の金属系ナノ粒子を溶媒中で攪拌した懸濁液に、これと同種の金属からなる金属化合物の粉末(原料粉)を導入して、上記加熱工程を繰り返すと、原料粉から金属系ナノ粒子への変換が起こる。すなわち、最初の加熱工程で生成された少量の金属系ナノ粒子と同種・同サイズの金属系ナノ粒子が、数倍から10倍以上の高い効率で生成される。その様子は、あたかも同種・同サイズの金属系ナノ粒子が複製されるかのごとくであることから、本明細書では、これを「自己触媒的増殖機能」とよぶ。この一連の過程を繰り返すことにより、容易に高濃度の金属系ナノ粒子分散液が得られる。 First, the basic procedure for producing metal-based nanoparticles in the present invention will be described.
(Procedure for producing metal-based nanoparticles)
When a raw material powder made of metal oxide is heated in a solvent at a predetermined temperature in a non-oxidizing atmosphere, most of the raw material powder is simply converted into a metal oxide powder that remains unchanged or has a significantly reduced oxygen ratio. However, a small amount of metal-based nanoparticles (1% to several percent (mass percent) in proportion) are produced at the same time.
When a metal compound powder (raw material powder) composed of the same kind of metal is introduced into a suspension obtained by stirring a small amount of metal-based nanoparticles thus produced in a solvent, and the heating step is repeated, Conversion from raw powder to metallic nanoparticles occurs. That is, metal nanoparticles having the same kind and size as the small amount of metal nanoparticles generated in the first heating step are generated with high efficiency of several times to 10 times or more. This state is as if the same type and size of metal-based nanoparticles are replicated. In this specification, this is referred to as “autocatalytic growth function”. By repeating this series of processes, a high-concentration metal-based nanoparticle dispersion can be easily obtained.
S1 金属化合物の粉末を、所定の溶媒中に懸濁させる工程と、
S2 その懸濁液を、不活性ガスもしくは水素ガスの雰囲気下で(好ましくは、不活性ガスもしくは水素ガスを通じながら)所定の温度で加熱する工程という、単純な2つの工程から構成される。この生成された金属系ナノ粒子が、加熱工程において自己触媒的増殖機能を有する場合には、必要に応じて原料粉を逐次追加しながら加熱工程を繰り返すことにより、高濃度の金属系ナノ粒子分散液を大量かつ安価に製造できる。 As described above, for the purpose of producing high-quality metallic nanoparticles with improved dispersion stability in large quantities and at low cost, the method of the present invention basically includes
Suspending the powder of the S1 metal compound in a predetermined solvent;
S2 The suspension is composed of two simple steps of heating the suspension at a predetermined temperature in an atmosphere of an inert gas or hydrogen gas (preferably through an inert gas or hydrogen gas). When the generated metal-based nanoparticles have an autocatalytic growth function in the heating process, high-concentration metal-based nanoparticle dispersion is achieved by repeating the heating process while sequentially adding raw material powder as necessary. A large amount of liquid can be manufactured at low cost.
上記原料を用いて、本発明の金属系ナノ粒子及び金属系ナノ粒子分散液は、次のようにして製造される。 (First embodiment)
Using the raw materials, the metal-based nanoparticles and the metal-based nanoparticle dispersion of the present invention are produced as follows.
原料粉として、福田金属箔粉工業(株)製の酸化銀微粉末を使用し、溶媒として、和光純薬工業(株)製γ-ブチロラクトン特級試薬を用いた。内容量10mLのガラス容器に5mLの溶媒を入れ、これに約40mgの原料粉を投入して、マグネチックスターラーによる攪拌と、毎分約20mLの窒素ガスバブリングによる脱気条件のもとで、ホットプレートを用いて約135℃で15分加熱した。次に、これを室温付近まで冷却後、沈降物を遠心分離で取り除き、得られた銀ナノ粒子分散液の状態を、その一部を適宜希釈して主に、浜松ホトニクス(株)製のマルチチャネルアナライザー(PMA11)を用いて、吸収分光法で解析した。その後、同分散液に、再び原料粉を追加し、同様の工程を計8回繰り返した。但し、最後の8回目だけは、原料粉を約2倍に増やし、投入量は70mgとした。 -Example 1-
Silver oxide fine powder manufactured by Fukuda Metal Foil Powder Co., Ltd. was used as the raw material powder, and γ-butyrolactone special grade reagent manufactured by Wako Pure Chemical Industries, Ltd. was used as the solvent.
実施例1と同じ条件で、原料粉として、和光純薬工業(株)製の酸化銀微粉末を使用した。実施例1で使用した原料粉と比べて、その粒子サイズが大きいという違いがある。
図5は、一工程あたり、約40mgの原料粉を用いて、計7回の工程を繰り返したときの、図1に対応するスペクトルである。但し最後の7回目の工程では、原料粉の投入量を200mgとした。初工程~3回目の工程で生成した銀ナノ粒子は実施例1と比べてむしろ向上した。一方、その後の工程では、一工程あたりの銀ナノ粒子は、約5mgと、実施例1の場合より低下し、原料から銀ナノ粒子への変換率は約10%に止まった。この比率は、最後の7回目の工程で原料粉の投入量を200mgに増やした場合にも変わらなかった。この結果は、比較的初期の工程では、むしろ粒子サイズが大きな原料粉を選択することにより、銀ナノ粒子の生成効率が向上することを示唆している。特に初工程では、原料粉の大半がナノ粒子以外の沈降成分となり、この過程がナノ粒子生成過程と競合する。サイズの大きな原料粉では、この競争過程の進行速度が比較的遅いため、その分、ナノ粒子生成の効率が向上するものと考えられる。 -Example 2-
Silver oxide fine powder manufactured by Wako Pure Chemical Industries, Ltd. was used as the raw material powder under the same conditions as in Example 1. Compared to the raw material powder used in Example 1, there is a difference that the particle size is large.
FIG. 5 is a spectrum corresponding to FIG. 1 when a total of seven steps are repeated using about 40 mg of raw material powder per step. However, in the final seventh step, the amount of raw material powder was 200 mg. The silver nanoparticles produced in the first to third steps were rather improved as compared with Example 1. On the other hand, in the subsequent steps, the silver nanoparticles per step was about 5 mg, which was lower than in the case of Example 1, and the conversion rate from the raw material to silver nanoparticles was only about 10%. This ratio did not change even when the input amount of the raw material powder was increased to 200 mg in the final seventh step. This result suggests that the generation efficiency of silver nanoparticles is improved by selecting a raw material powder having a relatively large particle size in a relatively initial step. In particular, in the initial process, most of the raw material powder becomes a sediment component other than nanoparticles, and this process competes with the nanoparticle generation process. Since the raw material powder having a large size has a relatively slow progress in this competitive process, it is considered that the efficiency of nanoparticle generation is improved accordingly.
別法であらかじめ作成した銀ナノ粒子の自己触媒的増殖機能の有無を調べるために、非特許文献1に記載されたレーザー法を用いて作成した銀ナノ粒子を使用した。その任意量を、種粒子として、初工程において原料粉と共に添加した以外は、条件は、実施例1と同じである。但し工程の繰り返し回数は計4回とした。
図6(a)は、このときに得られた一連の吸収スペクトルである。図1や図4と異なり、工程数が増えるにつれて、1回の工程で得られる銀ナノ粒子の量がむしろ減少した。また同時に、スペクトルのピーク位置が次第に長波長側にシフトしていることがわかる。これは、各工程で、原料粉から新たな銀ナノ粒子が生成したのではなく、単に、あらかじめ添加した種粒子が次第に成長したことを意味し、そのサイズがある限界を超えると、更なる成長が起こらなくなるだけでなく、自己触媒的増殖機能も失われることを示唆している。 -Example 3-
In order to examine the presence or absence of the autocatalytic growth function of silver nanoparticles prepared in advance by another method, silver nanoparticles prepared using the laser method described in Non-Patent Document 1 were used. The conditions are the same as in Example 1 except that the arbitrary amount is added as seed particles together with the raw material powder in the first step. However, the process was repeated a total of four times.
FIG. 6A shows a series of absorption spectra obtained at this time. Unlike FIG.1 and FIG.4, the quantity of the silver nanoparticle obtained by one process decreased rather as the number of processes increased. At the same time, it can be seen that the peak position of the spectrum is gradually shifted to the longer wavelength side. This does not mean that new silver nanoparticles were generated from the raw material powder in each step, but simply that the seed particles that had been added in advance gradually grew. When the size exceeded a certain limit, further growth occurred. Suggests that autocatalytic growth is lost as well.
原料粉として、和光純薬工業(株)製の水酸化銅粉末を使用し、溶媒として、和光純薬工業(株)γ-ブチロラクトン特級試薬を用いた。内容量10mLのガラス容器に5mLの溶媒を入れ、これに約60mgの水酸化銅を投入して、マグネチックスターラーによる攪拌と、毎分約20mLの窒素ガスバブリングによる脱気条件のもとで、ホットプレートを用いて、γ-ブチロラクトンの沸点に近い170~180℃で、20分加熱した。室温付近まで冷却後、沈降物を遠心分離で取り除き、分散液の状態を吸収分光法で解析した。 -Example 4-
A copper hydroxide powder manufactured by Wako Pure Chemical Industries, Ltd. was used as a raw material powder, and a γ-butyrolactone special grade reagent manufactured by Wako Pure Chemical Industries, Ltd. was used as a solvent. Into a glass container with an internal volume of 10 mL, 5 mL of solvent is added, and about 60 mg of copper hydroxide is added thereto. Under stirring conditions with a magnetic stirrer and degassing conditions with about 20 mL of nitrogen gas bubbling per minute, Using a hot plate, it was heated at 170-180 ° C., which is close to the boiling point of γ-butyrolactone, for 20 minutes. After cooling to near room temperature, the sediment was removed by centrifugation, and the state of the dispersion was analyzed by absorption spectroscopy.
実施例4と同じ条件で、種粒子として、あらかじめレーザー法で作成した銅ナノ粒子を酸化して得られた酸化銅(I)ナノ粒子を用いた。図8に示すように、その結果は、本発明を特徴づける自己触媒的増殖機能の本質的な役割をより明確に示している。すなわち図8において、本実施例で用いた種粒子のスペクトルは、500nm付近から短波長側に向かって比較的鋭い立ち上りを示し、長波長側の吸収が小さい。これは、粒径10nmレベルの小さな酸化銅(I)ナノ粒子の性質を表している。更に、二回目の工程以降で、はるかに高い効率で生成するナノ粒子もまた、同様な性質を有していることが図8のスペクトルから読み取れる。実施例4に対する図7と、本実施例に対する図8の実験条件の違いは、種粒子の違いのみである。にも拘わらず、繰り返しの工程で生成するナノ粒子にこのような大きな差が現れることは、種粒子があたかも何らかの遺伝子的情報を備えているかのごとく、同種・同サイズのナノ粒子が後続する繰り返し工程で増殖する自己触媒的増殖機能と密接に関連する機構を裏付けている。 -Example 5
Under the same conditions as in Example 4, copper (I) oxide nanoparticles obtained by oxidizing copper nanoparticles previously prepared by a laser method were used as seed particles. As shown in FIG. 8, the results more clearly show the essential role of the autocatalytic growth function that characterizes the present invention. That is, in FIG. 8, the spectrum of the seed particles used in this example shows a relatively sharp rise from the vicinity of 500 nm toward the short wavelength side, and the absorption on the long wavelength side is small. This represents the nature of small copper (I) oxide nanoparticles with a particle size of 10 nm. Furthermore, it can be read from the spectrum of FIG. 8 that nanoparticles produced with much higher efficiency after the second step also have similar properties. The difference in the experimental conditions of FIG. 7 for Example 4 and FIG. 8 for the present example is only the difference in seed particles. Nevertheless, such a large difference appears in the nanoparticles generated in the repetition process, as if the seed particles had some kind of genetic information. It supports a mechanism closely related to the autocatalytic growth function that grows in the process.
加熱しないこと以外は実施例1と同じ条件で実施した。1回目の工程実施後の液を、吸収分光法で解析した。その結果、銀ナノ粒子に由来するプラズモンのスペクトルは見られず、銀ナノ粒子が生成しないことがわかった。また、工程を8回目まで繰り返したが、いずれも銀ナノ粒子が生成しないことがわかった。原料粉を酸化銀、溶媒をγ-ブチロラクトン、雰囲気を窒素雰囲気とする条件において、銀ナノ粒子の有意な生成を確認できたのは、100℃以上の加熱条件を用いた場合である。
-比較例2-
実施例1と同じ条件で、攪拌は行うが、窒素ガスをバブリングせずに実施した。1回目及び2回目の実施後の液を、吸収分光法で解析したところ、図9に示したように、順調に銀ナノ粒子が生成するように思えた。ところが、3回目以降の実施後では、銀ナノ粒子の量が増えるどころか、逆にプラズモン強度が低下し、初期に生成した銀ナノ粒子の多くが系から失われることがわかった。実施例1や本比較例のように、130℃以上の温度に加熱された溶媒からは、溶媒の蒸発とともに溶存酸素も系から除去され、初回及び2回目の工程においては、非酸化性の雰囲気がかろうじて維持されるが、銀ナノ粒子の生成に伴い、原料粉からは絶えず酸素が放出され、それが次第に系内に蓄積するにいたって、ついには銀ナノ粒子の生成が抑制され、一部は酸化により失われることがわかった。
-比較例3-
比較例2で示された非酸化性雰囲気の重要性を更に確認するために、実施例1と同じ条件で、窒素ガスの代わりに空気をバブリングして実施した。その結果、初回の工程を含めて、銀ナノ粒子に由来するプラズモンのスペクトルは見られず、銀ナノ粒子がもはや生成しないことがわかった。 -Comparative Example 1-
It implemented on the same conditions as Example 1 except not heating. The liquid after the first step was analyzed by absorption spectroscopy. As a result, it was found that the spectrum of plasmons derived from silver nanoparticles was not observed, and silver nanoparticles were not generated. Moreover, although the process was repeated to the 8th time, it turned out that silver nanoparticle does not produce | generate all. Under the conditions where the raw material powder is silver oxide, the solvent is γ-butyrolactone, and the atmosphere is a nitrogen atmosphere, significant formation of silver nanoparticles was confirmed when heating conditions of 100 ° C. or higher were used.
-Comparative Example 2-
Stirring was performed under the same conditions as in Example 1, but the nitrogen gas was not bubbled. When the liquid after the 1st time and the 2nd time was analyzed by the absorption spectroscopy, it seemed that the silver nanoparticles were generated smoothly as shown in FIG. However, after the third and subsequent implementations, it was found that, instead of increasing the amount of silver nanoparticles, the plasmon intensity decreased, and many of the silver nanoparticles generated at the beginning were lost from the system. As in Example 1 and this comparative example, from the solvent heated to a temperature of 130 ° C. or higher, dissolved oxygen is also removed from the system as the solvent evaporates. In the first and second steps, a non-oxidizing atmosphere is used. However, as the generation of silver nanoparticles, oxygen is constantly released from the raw material powder and gradually accumulates in the system. Was found to be lost by oxidation.
-Comparative Example 3-
In order to further confirm the importance of the non-oxidizing atmosphere shown in Comparative Example 2, air was bubbled instead of nitrogen gas under the same conditions as in Example 1. As a result, it was found that the plasmon spectrum derived from the silver nanoparticles was not seen including the first step, and the silver nanoparticles were no longer formed.
以上のように、本発明は工業的に大きな波及効果が期待でき、その産業上の利用可能性は極めて大きい。 The metal-based nanoparticles according to the present invention are based on a specific action of an autocatalytic growth function, a container for dispersing a raw metal compound powder in a solvent selected as appropriate, and a gas supply that provides a non-oxidizing atmosphere, In addition, since it can be produced in a large amount and at a low cost only by a simple heating process, it is expected to be widely applied to ink for forming conductors of electronic circuit devices.
As described above, the present invention can be expected to have a large industrial ripple effect, and its industrial applicability is extremely large.
Claims (14)
- 金属化合物の粉末と溶媒からなる懸濁液を、非酸化性ガス雰囲気下で加熱して得られる、凝集抑制物質なしでも高い分散安定性を保持することができることを特徴とする金属系ナノ粒子分散液。 Metal-based nanoparticle dispersion characterized by maintaining a high dispersion stability even without a coagulation inhibitor obtained by heating a suspension of a metal compound powder and a solvent in a non-oxidizing gas atmosphere liquid.
- 金属化合物の粉末と溶媒からなる懸濁液に、更に、該金属化合物と同じ金属種の金属系ナノ粒子を含有する懸濁液を、非酸化性ガス雰囲気下で加熱して得られる、凝集抑制物質なしでも高い分散安定性を保持することができることを特徴とする金属系ナノ粒子分散液。 Aggregation suppression obtained by heating a suspension of metal compound powder and solvent to a suspension containing metal nanoparticles of the same metal species as the metal compound in a non-oxidizing gas atmosphere A metal-based nanoparticle dispersion, which can maintain high dispersion stability without a substance.
- 粒子径が50nm以下からなり、粒子径分布が略ガウス分布であると共に、粒子の少なくとも一部に単結晶ファセットを有することを特徴とする請求項1又は2記載の金属系ナノ粒子分散液。 3. The metal-based nanoparticle dispersion liquid according to claim 1, wherein the particle size is 50 nm or less, the particle size distribution is substantially Gaussian distribution, and at least a part of the particles has a single crystal facet.
- 請求項1乃至3のいずれか1項に記載の金属系ナノ粒子分散液であって、前記金属系ナノ粒子の濃度が20質量%以上に濃縮されていると共に、前記金属系ナノ粒子に由来する特定のプラズモン吸収バンドを有することを特徴とする高濃度の金属系ナノ粒子分散液。 The metal-based nanoparticle dispersion according to any one of claims 1 to 3, wherein the concentration of the metal-based nanoparticles is concentrated to 20% by mass or more and is derived from the metal-based nanoparticles. A high-concentration metal-based nanoparticle dispersion characterized by having a specific plasmon absorption band.
- 金属化合物粉末と溶媒からなる懸濁液を、非酸化性ガス雰囲気下で加熱することを特徴とする金属系ナノ粒子分散液の製造方法。 A method for producing a metal-based nanoparticle dispersion, which comprises heating a suspension comprising a metal compound powder and a solvent in a non-oxidizing gas atmosphere.
- 金属、合金又は金属化合物からなる金属系ナノ粒子を種粒子として溶媒中に分散させた分散液と、前記種粒子と同種の金属からなる金属化合物粉末とを混合する工程と、この工程で得られた混合物を非酸化性ガス雰囲気下で加熱する工程とを含む、金属系ナノ粒子分散液の製造方法。 A step of mixing a dispersion in which metal-based nanoparticles made of metal, alloy or metal compound are dispersed in a solvent as seed particles, and a metal compound powder made of the same kind of metal as the seed particles, and obtained in this step. And a step of heating the mixture in a non-oxidizing gas atmosphere.
- 前記加熱の温度と前記溶媒の沸点が、いずれも100℃以上であることを特徴とする請求項5又は6記載の金属系ナノ粒子分散液の製造方法。 The method for producing a metal-based nanoparticle dispersion according to claim 5 or 6, wherein the heating temperature and the boiling point of the solvent are both 100 ° C or higher.
- 前記溶媒は、γ-ブチロラクトン、ジアセトンアルコール、シクロヘキサノン、その他のケトン類もしくはカルボニル化合物、又は、テトラデカンその他の高沸点アルカン類であることを特徴とする請求項5乃至7のいずれか1項に記載の金属系ナノ粒子分散液の製造方法。 8. The solvent according to claim 5, wherein the solvent is γ-butyrolactone, diacetone alcohol, cyclohexanone, other ketones or carbonyl compounds, or tetradecane or other high boiling point alkanes. A method for producing a metal-based nanoparticle dispersion liquid.
- 前記溶媒中に金属、合金又は金属化合物からなる金属系ナノ粒子を種粒子として分散させた分散液と、前記種粒子と同種の金属からなる金属化合物粉末とを混合する工程とこの工程で得られる混合物を非酸化性ガス雰囲気下で加熱する工程とを、複数回繰り返すことを特徴とする請求項6乃至8のいずれか1項に記載の金属系ナノ粒子分散液の製造方法。 A step of mixing a dispersion obtained by dispersing metal-based nanoparticles made of metal, alloy or metal compound as seed particles in the solvent, and a metal compound powder made of the same kind of metal as the seed particles is obtained in this step. The method for producing a metal-based nanoparticle dispersion according to any one of claims 6 to 8, wherein the step of heating the mixture in a non-oxidizing gas atmosphere is repeated a plurality of times.
- 前記金属ナノ粒子の種粒子の製造方法は、純金属、合金又は金属化合物の微粉末を溶媒中に懸濁させ、その懸濁液にレーザー光を照射する工程からなることを特徴とする請求項6記載の金属ナノ粒子分散液の製造方法。 The method for producing seed particles of the metal nanoparticles comprises a step of suspending fine powder of pure metal, alloy or metal compound in a solvent and irradiating the suspension with laser light. 6. A method for producing a metal nanoparticle dispersion according to 6.
- 前記金属系ナノ粒子分散液の製造方法は、製造工程とは異なる溶媒に置換する工程を更に備えることを特徴とする請求項5又は6記載の金属系ナノ粒子分散液の製造方法。 The method for producing a metal-based nanoparticle dispersion according to claim 5 or 6, further comprising a step of substituting with a solvent different from the production process.
- 前記金属系ナノ粒子分散液の製造方法は、最終工程において、溶媒を蒸発することにより金属系ナノ粒子の濃度を高める工程を更に備えることを特徴とする請求項5又は6記載の金属系ナノ粒子分散液の製造方法。 The metal-based nanoparticle dispersion according to claim 5 or 6, wherein the method for producing the metal-based nanoparticle dispersion further comprises a step of increasing the concentration of the metal-based nanoparticle by evaporating the solvent in the final step. A method for producing a dispersion.
- 請求項1乃至4のいずれか1項に記載の金属系ナノ粒子分散液を主成分とする導体形成用インク。 An ink for forming a conductor comprising the metal-based nanoparticle dispersion liquid according to any one of claims 1 to 4 as a main component.
- 請求項13記載の導体形成用インクを用いて、インクジェット法、スピン塗布法、凸版印刷法、凹版印刷法、又はスクリーン印刷法により、導体を形成する成膜方法。 A film forming method for forming a conductor using the ink for forming a conductor according to claim 13 by an inkjet method, a spin coating method, a relief printing method, an intaglio printing method, or a screen printing method.
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