KR101166001B1 - Metal-containing fine particle, liquid dispersion of metal-containing fine particle, and conductive metal-containing material - Google Patents

Abstract

The present invention relates to a metal-containing fine particle having good dispersion stability surface-coated by a dispersant vaporizable even at low temperature firing, a fine particle dispersion in which the metal-containing fine particles are dispersed, and a conductive metal containing excellent volume resistivity formed using the fine particle dispersion. Provide the material.

More particularly, the metal-containing fine particles surface-coated with at least two dispersants having different vaporization temperatures are provided.

Description

METAL-CONTAINING FINE PARTICLE, LIQUID DISPERSION OF METAL-CONTAINING FINE PARTICLE, AND CONDUCTIVE METAL-CONTAINING MATERIAL}

TECHNICAL FIELD This invention relates to the manufacturing method of the microparticles | fine-particles dispersion liquid, the microparticle dispersion liquid in which metal containing microparticles | fine-particles were disperse | distributed, and the microparticle dispersion liquid, and the electrically conductive metal containing material formed with the microparticle dispersion liquid.

In recent years, various methods of forming a conductor by mutually sintering metal fine particles by forming a pattern using a fine particle dispersion in which metal-containing fine particles are dispersed in a liquid and then heat-processing (hereinafter also referred to simply as "firing") It is considered. As an example, the method of forming and repairing circuit patterns, such as printed wiring, forming interlayer wiring in a semiconductor package, joining a printed wiring board and an electronic component, etc. by the inkjet printing method (for example, refer patent document 1), conventionally Method of joining metals instead of the soldering method (for example, refer to Patent Document 2), a method of forming a conductive film which can be replaced with a plated film in the field of electronic materials (see, for example, Patent Document 3), and the like. Can be mentioned.

The above-mentioned method utilizes the property of surface melting phenomenon of the metal particle conventionally known (for example, refer nonpatent literature 1). In general, it is known that the surface melting phenomenon of metal particles is caused by abnormal lattice vibration of particle surface atoms, and the smaller the particle diameter and the higher the surface atom ratio, the lower the surface melting temperature. For example, in the case of silver, melting | fusing point of a bulk body is about 970 degreeC, but it is known that surface melting arises from about 80 degreeC in the case of microparticles (colloid) of about 10 nm in diameter. Since the surface fusion phenomenon depends on the particle diameter of the metal particles, unless the particles are completely fixed, the surface melting phenomenon occurs even if the metal particles have a predetermined particle diameter even in the associated state.

Generally, in the case of dispersing the metal fine particles in a liquid, a dispersant is used to prevent aggregation. Here, in order to disperse | distribute metal microparticles | fine-particles favorably in an organic solvent, it is necessary to form a big three-dimensional obstacle on the surface of the microparticles | fine-particles. However, if a large steric hindrance is to be obtained, it is necessary to polymerize the dispersant or to increase the amount of the dispersant added. In addition, in the case of forming a conductor by using a fine particle dispersion in which metal fine particles are dispersed, if a polymerized dispersant is used or the addition amount of the dispersant is increased, the dispersant cannot be removed unless it is caused by baking at a high temperature. There is a problem that conductivity becomes difficult to be obtained.

Moreover, the lower the firing temperature is, the more preferable the problem is in the heat resistance of the element in the wiring of the printed wiring board and the wiring in the semiconductor package.

Patent Document 1: Japanese Unexamined Patent Publication No. 2002-324966

Patent Document 2: Japanese Unexamined Patent Publication No. 2002-126869

Patent Document 3: Japanese Unexamined Patent Publication No. 2002-334618

[Non-Patent Document 1] J. Sol-Gel Science and Technology, The Netherlands, Kluwer Academic Publishers, 2001, 22, p.151- 166

DISCLOSURE OF INVENTION

Problems to be solved by the invention

Therefore, the present invention is excellent in volume resistivity formed by using metal-containing fine particles having good dispersion stability coated with a dispersant vaporizable even at low temperature firing, a fine particle dispersion in which the metal-containing fine particles are dispersed, and the fine particle dispersion. It is an object to provide a conductive metal-containing material.

Means for solving the problem

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in order to achieve the said objective, the metal containing microparticles | fine-particles surface-coated with the at least 2 sort (s) of dispersing agent which differ in vaporization temperature have favorable dispersion stability, and used the microparticle dispersion which this metal-containing compound disperse | distributed. The electroconductive metal containing material which can be formed by baking at low temperature (150-210 degreeC) discovered that it was excellent in volume resistivity, and came to achieve this invention. That is, this invention has the following summary.

(1) Metal-containing fine particles (first aspect) surface-coated with at least two kinds of dispersants having different vaporization temperatures.

(2) As metal-containing microparticles | fine-particles disperse | distributed to the microparticle dispersion liquid used for baking at predetermined | prescribed baking temperature,

Metal-containing microparticles | fine-particles as described in said (1) surface-coated with the dispersing agent vaporized below the said baking temperature, and the dispersing agent vaporized above the said baking temperature.

(3) A fine particle dispersion (second embodiment) in which the metal-containing fine particles described in the above (1) or (2) are dispersed in a water-insoluble organic liquid.

(4) As a production method for producing the fine particle dispersion according to the above (3),

Adding water to a water-soluble metal-containing compound to obtain an aqueous solution containing metal ions,

Adding a water-insoluble organic liquid in which at least two kinds of dispersants having different vaporization temperatures are dissolved into the aqueous solution;

A method for producing a fine particle dispersion comprising the step of reducing the metal ions by adding a reducing agent while stirring the organic liquid and producing metal-containing fine particles surface-coated with at least two kinds of dispersants having different vaporization temperatures. Third aspect).

(5) As a manufacturing method for producing the fine particle dispersion according to the above (3),

Obtaining an aqueous solution containing citrate ions and ferric ions,

By adding while stirring the aqueous solution containing the ion of 1 or more types of metals chosen from the group which consists of gold, silver, platinum, palladium, tungsten, tantalum, bismuth, lead, indium, tin, titanium, and aluminum, Reducing the metal ions to obtain metal-containing fine particles;

The metal containing surface-coated with the at least 2 type of dispersing agent from which the vaporization temperature differs by adding to the liquid containing the said metal containing microparticles, stirring, the water-insoluble organic liquid which melt | dissolved the at least 2 type of dispersing agent from which the said vaporization temperature differs, stirring. A method for producing a particulate dispersion comprising a step of producing particulates.

(6) The volume resistivity formed by apply | coating the fine particle dispersion as described in said (3) to a to-be-coated object, and baking at the temperature between the highest vaporization temperature and the lowest vaporization temperature among the said at least 2 types of dispersing agents is 60 microohm-cm or less. Conductive metal-containing material (fourth aspect).

Effects of the Invention

As described below, according to the present invention, metal-containing fine particles having good dispersion stability surface-coated with a dispersant vaporizable even at low temperature firing, a fine particle dispersion in which the metal-containing fine particles are dispersed, and the fine particle dispersion are formed. It is useful because it is possible to provide a conductive metal-containing material with excellent volume resistivity.

In particular, by using the particulate dispersion according to the second aspect of the present invention (hereinafter, simply referred to as "microparticle dispersion of the present invention") as ink of the inkjet printing method, formation and repair of circuit patterns such as printed wiring, and the like in a semiconductor package Formation of interlayer wiring and bonding of a printed wiring board and an electronic component are possible at low temperatures, and the material formed is also very useful in that it has excellent conductivity.

Carrying out the invention  Best form for

EMBODIMENT OF THE INVENTION Below, this invention is demonstrated in detail.

Metal-containing fine particles (hereinafter, also referred to simply as "metal-containing fine particles of the present invention") according to the first aspect of the present invention are metal-containing fine particles surface-coated with at least two kinds of dispersants having different vaporization temperatures. Specifically, as a metal-containing fine particle dispersed in the fine particle dispersion used for baking at a predetermined baking temperature, the dispersing agent vaporized below the baking temperature (henceforth simply called a "first dispersing agent"), and its baking temperature or more Metal-containing microparticles | fine-particles surface-coated by the dispersing agent (henceforth simply a "2nd dispersing agent") vaporized in the above are preferable.

Here, "firing temperature" means the baking at the time of forming the electroconductive metal containing material (henceforth simply called "the electroconductive metal containing material of this invention") concerning the 4th aspect of this invention mentioned later, specifically, The temperature at the time of baking after apply | coating the fine particle dispersion of this invention to a to-be-coated object can be said, and it can set arbitrarily to a predetermined range. As mentioned above, it is preferable that it is the range of 150-210 degreeC from the viewpoint of the heat resistance of the element in the board | substrate in wiring of a printed wiring board, or the wiring in a semiconductor package, and it is more preferable that it is the range of 150-200 degreeC. Do.

In addition, in this invention, baking means the process of dissociating the dispersing agent which coat | covers the surface of metal containing microparticles | fine-particles, and fusing the metal containing microparticles | fine-particles after dispersing agent dissociation.

In addition, "coated" means that at least one part of the surface of metal containing microparticles | fine-particles is a state covered with the dispersing agent. Specifically, at least a part of the surface of the metal-containing fine particles refers to a state in which an organic compound having a substituent containing nitrogen, oxygen or a sulfur atom is bonded as a substituent capable of bonding with a metal element contained in the metal-containing fine particles. In addition, the coating | coating with a dispersing agent is a low vaporization temperature (30- ~) in the manufacturing method of the fine particle dispersion which concerns on the 3rd aspect of this invention mentioned later (it is only hereafter called "the manufacturing method of the fine particle dispersion of this invention"). 60 ° C.) When only the dispersant is used, or when the dispersant is prepared without using a dispersant, or when an organic substance having no substituent groupable with a metal element is used instead of the dispersant, the dispersant may be effectively coated on the surface of the metal-containing fine particles. And metal-containing fine particles are agglomerated and a stable fine particle dispersion cannot be produced. In contrast, in the present invention, it can also be confirmed from the fact that a fine particle dispersion in which metal-containing fine particles are dispersed can be produced.

The metal-containing fine particles of the present invention include gold (Au), silver (Ag), copper (Cu), platinum (Pt), palladium (Pd), tungsten (W), nickel (Ni), tantalum (Ta), bismuth ( It contains at least one metal selected from the group consisting of Bi), lead (Pb), indium (In), tin (Sn), titanium (Ti), and aluminum (Al). Especially, it is especially preferable to contain Au, Ag, Cu, or Ni, and it is most preferable to contain Cu.

In addition, in this invention, a "metal containing fine particle" means metal fine particle itself (for example, Au colloid, Ag colloid etc.), and hydrogenated metal fine particle (for example, copper hydride copper (CuH) colloid etc.) It is a word of concept that includes together.

Therefore, the metal-containing microparticles | fine-particles of this invention may be Au colloid, Ag colloid, etc. which were surface-coated with at least 2 sort (s) of dispersing agent different from vaporization temperature, CuH colloid, etc. may be sufficient.

Next, the dispersant is described in detail.

As at least 2 sort (s) of dispersing agent in which the vaporization temperature which coat | covers the surface of the metal containing fine particle of this invention differs, a 1st dispersing agent and a 2nd dispersing agent are mentioned as mentioned above. These are organic compounds which have a substituent containing a nitrogen, oxygen, or sulfur atom as a substituent which can coordinately bond with the metal element contained in metal containing microparticles | fine-particles.

Here, "a 1st dispersing agent" means the dispersing agent which has vaporization temperature less than a baking temperature, and similarly, "a 2nd dispersing agent" means the dispersing agent which has a vaporization temperature above baking temperature. In addition, in this invention, vaporization temperature means the temperature at which 50% of an injection mass vaporizes when it measures using the thermogravimetric method on the measurement conditions shown below.

[Measuring conditions]

Measuring start temperature: 25 ℃

Heating rate: 10 ℃ / min

Atmosphere: in nitrogen (flow rate: 20 mL / min)

Injection weight: 10mg

Cell used: aluminum (5 μL)

As such a dispersing agent, as above-mentioned, if it is an organic compound which has a substituent containing a nitrogen, oxygen, or sulfur atom as a substituent which can coordinate coordination with the metal element contained in metal containing microparticles | fine-particles, it will not specifically limit, It will have 4-25 carbon atoms. It is preferable, and it is more preferable that it is 8-23. If carbon number range is this range, since there exists thermal stability, steam pressure is appropriate, and handling property improves, it is preferable. If the carbon number is in this range, it can be sufficiently vaporized even by baking at low temperature, and the dispersion stability of the metal-containing fine particles surface-coated with such a dispersant is also preferable.

Moreover, it is preferable that the said dispersing agent may be either unsaturated or saturated, and has a linear long chain (for example, a decyl group, a dodecyl group, etc.).

Moreover, it is preferable that the vaporization temperature of the said dispersing agent is 125-235 degreeC.

Specifically, the compound which has substituents, such as an amino group and an amide group, is mentioned as an organic compound which has a substituent containing a nitrogen atom. As an organic compound which has a substituent containing an oxygen atom, the compound which has substituents, such as a hydroxyl group and an ether type oxy group (-O-), is mentioned, As an organic compound which has a substituent containing a sulfur atom, a sulfanyl group (- The compound which has substituents, such as SH) and a sulfide type sulfanediyl group (-S-), is mentioned.

More specifically, as a compound which has substituents, such as an amino group and an amide group, octylamine (155 degreeC), decylamine (170 degreeC), dodecylamine (180 degreeC), tetradecylamine (190 degreeC), hexadecylamine (200 ° C.), octadecylamine (205 ° C.), methyloctadecylamine (210 ° C.), dimethyloctadecylamine (215 ° C.), oleylamine (205 ° C.), benzylamine (140 ° C.), laurylamide, Stearylamide, oleylamide and the like. As a compound which has substituents, such as a hydroxyl group and ether type oxy group (-O-), dodecanediol, hexadecanediol, dodecanoic acid (200 degreeC), stearic acid (225 degreeC), oleic acid (225 degreeC), linoleic acid, Linolenic acid, dodecanedione, dibenzoylmethane, ethylene glycol monodecyl ether (200 ° C.), diethylene glycol monodecyl ether, triethylene glycol monodecyl ether, tetraethylene glycol monodecyl ether, ethylene glycol monododecyl ether (210 ° C.) ), Diethylene glycol monododecyl ether, triethylene glycol monododecyl ether, tetraethylene glycol monododecyl ether, ethylene glycol monocetyl ether (225 ° C), diethylene glycol monocetyl ether, and the like. As a compound which has substituents, such as a sulfanyl group (-SH) and a sulfide type sulfanediyl group (-S-), decanthiol (190 degreeC), dodecane thiol (205 degreeC), and detradecane thiol (220 degreeC) , Trimethylbenzyl mercaptan, butylbenzyl mercaptan, hexyl sulfide and the like. In addition, the number in parentheses is the vaporization temperature measured by the above-mentioned measurement conditions.

Among these dispersants, in the present invention, two or more kinds of dispersants having different vaporization temperatures may be appropriately selected, and specifically, the first dispersant and the second dispersant may be appropriately selected and used from these dispersants.

For example, when baking temperature is 150 degreeC, the combination of benzylamine and octylamine, the combination of benzylamine and decylamine, the combination of benzylamine and dodecylamine, etc. are illustrated. When baking temperature is 180 degreeC, the combination of decylamine and tetradecylamine, the combination of octylamine and tetradecylamine, the combination of octylamine and dodecanoic acid, etc. are illustrated. When baking temperature is 190 degreeC, the combination of a dodecylamine and a dodecanoic acid, the combination of a dodecylamine and tetradecylamine, etc. are illustrated. When the baking temperature is 195 ° C, a combination of tetradecylamine and dodecanoic acid, a combination of tetradecylamine and hexadecylamine, and the like are exemplified. If the firing temperature is 200 ° C, the combination of dodecylamine and octadecylamine, the combination of dodecylamine and methyloctadecylamine, the combination of tetradecylamine and dimethyloctadecylamine, the combination of dodecylamine and dodecanethiol Is illustrated. When baking temperature is 210 degreeC, the combination of hexadecylamine and dimethyloctadecylamine, the combination of dodecanoic acid and tetradecanethiol, the combination of hexadecylamine and tetradecanethiol, etc. are illustrated.

In addition, in this invention, it is preferable that the difference of the baking temperature and the vaporization temperature of a 1st dispersing agent is 25 degrees C or less, and similarly, it is preferable that the difference of the baking temperature and the vaporization temperature of a 2nd dispersing agent is also 25 degrees C or less. Moreover, it is preferable that the difference of the vaporization temperature of a 1st dispersing agent and a 2nd dispersing agent is 30 degrees C or less.

The surface coating of the metal-containing fine particles by such a dispersant is preferably performed by adding the dispersant so that the total amount of the dispersant is 2 to 100 parts by mass, preferably 2 to 20 parts by mass in total. If it is the said range, since dispersion stability of the metal containing fine particle obtained becomes favorable, it is preferable.

Specifically, as shown in the method for producing the fine particle dispersion of the present invention or in the examples described later, the metal-containing fine particles produced by reduction using the wet method and the non-aqueous organic liquid in which the dispersant is dissolved are co-existed by stirring. Although the method of coating the surface of containing fine particles with a dispersing agent is illustrated preferably, what is called a dry method may be used.

Moreover, the ratio (injection mass ratio) of a 1st dispersing agent and a 2nd dispersing agent in the dispersing agent to be used is 60-95 mass% with respect to the total injection mass of a dispersing agent, Preferably it is 70-90 mass% Is preferably.

The metal-containing fine particles of the present invention surface-coated with such a dispersant have an average particle diameter of about 1 to 100 nm, and do not aggregate even if the fine particle dispersion in which the metal-containing fine particles are dispersed is left at room temperature for about one month. That is, the dispersion stability can be kept good, and can be stably present in the colloidal state.

In this invention, an average particle diameter is obtained using a transmission electron microscope (TEM) or a scanning electron microscope (SEM). In addition, the particle diameter of microparticles | fine-particles means the particle diameter of the primary particle observed, and an average particle diameter is defined as obtaining the average value of the particle diameter of 100 fine particles extracted randomly among the observed microparticles | fine-particles.

In addition, in the metal-containing fine particles of the present invention, the dispersant covering the surface is dissociated by firing, and the metal-containing fine particles after dissociating the dispersant are fused to form a bulk body. Thereby, the electroconductive metal containing material of this invention mentioned later will show electroconductivity and heat resistance.

The fine particle dispersion according to the second aspect of the present invention is a fine particle dispersion in which the metal-containing fine particles according to the first aspect of the present invention are dispersed in a water-insoluble organic liquid.

Here, it is preferable that the said organic liquid is low in polarity with favorable affinity with the dispersing agent which coat | covers the surface of the said metal containing microparticles | fine-particles. Moreover, also when forming the electroconductive metal containing material of this invention mentioned later, it is preferable to have thermal stability which evaporates comparatively fast by the heating after application | coating, and does not cause thermal decomposition.

Specifically as such an organic liquid, For example, hexane, heptane, octane, decane, dodecane, tetradecane, dodecene, tetradecene, cyclohexane, ethylcyclohexane, butylcyclohexane, cyclooctane, terpineol , Hexanol, octanol, cyclohexanol, toluene, xylene, ethylbenzene, mesitylene, butylbenzene, alpha terpene, gamma terpene, limonene, AF solvent (trade name, Nippon Petroleum Co., Ltd.) and the like. These may be used individually by 1 type and may use 2 or more types together.

In addition, since the fine particle dispersion of this invention is suitably selected according to the use, it does not specifically limit, It is preferable to add 20-500 mass parts of organic liquid with respect to 100 mass parts of said metal containing fine particles, 20-200 mass More preferably added. That is, it is preferable that it is 15-80 mass% with respect to the said organic liquid, and, as for the density | concentration of the said metal containing microparticles | fine-particles in the microparticle dispersion liquid of this invention, it is more preferable that it is 30-80 mass%.

If the density | concentration of a metal fine particle is this range, the electroconductivity of the electroconductive metal containing material of this invention obtained by apply | coating and baking the fine particle dispersion obtained can be fully ensured. Moreover, since the characteristics, such as a viscosity and surface tension of the fine particle dispersion obtained, become favorable and it becomes easy to apply | coat, it is preferable.

Moreover, additives (for example, a plasticizer, a thickener, etc.), an organic binder, etc. can be added to the fine particle dispersion of this invention as needed.

Although the use of the fine particle dispersion of this invention is not specifically limited, By using as an ink for the inkjet printing method, formation and repair of circuit patterns, such as a printed wiring, formation of interlayer wiring in a semiconductor package, bonding of a printed wiring board and an electronic component It becomes possible at low temperature, and the material formed is also very useful at the point which has the outstanding electroconductivity.

The manufacturing method of the fine particle dispersion which concerns on the 3rd aspect of this invention is a manufacturing method of manufacturing the fine particle dispersion which concerns on the 2nd aspect of this invention mentioned above, Comprising: Adding water to a water-soluble metal containing compound and containing metal ion The metal ion by adding the reducing agent with stirring, after the process of obtaining an aqueous solution, the process of adding the water-insoluble organic liquid which melt | dissolved the at least 2 sort (s) of dispersing agent from which the said vaporization temperature differs, and the organic liquid addition to this aqueous solution, And a process for producing metal-containing fine particles surface-coated with the dispersant.

When producing the metal-containing fine particles of the present invention, a suspension of water and oil (emulsion) by stirring an aqueous layer composed of an aqueous solution containing metal ions and an oil layer composed of at least two kinds of dispersants having different vaporization temperatures and organic liquids. To form. In the water of this suspension, metal ions are reduced by a reducing agent added separately to obtain metal-containing fine particles in a state before the surface is coated. It is thought that the obtained microparticles | fine-particles become the metal containing microparticles | fine-particles of this invention surface-coated with the said dispersing agent by covering the surface immediately with the said at least 2 sort (s) of dispersing agent melt | dissolved in oil, and are taken in and stabilized in oil.

After the metal-containing fine particles are produced in this way, the suspension is left to separate into two layers, an aqueous layer and an oil layer. By recovering the separated oil layer, a fine particle dispersion in which metal-containing fine particles are dispersed in a water-insoluble organic liquid can be obtained.

This fine particle dispersion can be used as so-called ink for forming a conductive metal containing material as it is or by adding another additive (for example, a plasticizer, a thickener, etc.) suitably.

Specific examples of the water-soluble metal-containing compound used in the method for producing the fine particle dispersion of the present invention include copper sulfate, copper chloride, copper acetate, copper bromide, copper iodide, copper citrate, and copper nitrate; Silver acetate, silver citrate, silver nitrate; Sodium chloride and gold chloride; Nickel bromide, nickel acetate, nickel nitrate, nickel chloride; Etc. are preferably illustrated.

Moreover, it is preferable to melt | dissolve so that the said metal containing compound may be 0.1-30 mass%. When the density | concentration of the aqueous solution which melt | dissolved the metal containing compound, ie, the aqueous solution containing metal ion, is in this range, since the production efficiency of the metal containing fine particle obtained becomes favorable and dispersion stability will also become favorable, it is preferable.

In the method for producing the fine particle dispersion of the present invention, for example, in order to obtain the CuH colloid described above, it is preferable to adjust the pH of the aqueous solution containing metal ions to 3 or less. Specifically, it is preferable to add an acid to an aqueous solution containing metal ions.

Specific examples of the acid added in order to adjust the pH to 3 or less include citric acid, malonic acid, maleic acid, phthalic acid, acetic acid, propionic acid, sulfuric acid, nitric acid, hydrochloric acid and the like. When pH is set to 3 or less, the metal ion in aqueous solution becomes easy to be obtained as metal containing microparticles | fine-particles by the action of the reducing agent added after that.

As a reducing agent, a metal hydride is preferable at the point which has a big reducing effect. Specifically, lithium hydride, potassium hydride, calcium hydride, lithium hydride, lithium borohydride, sodium borohydride, hydrazine, dimethylamine borane, etc. are mentioned, for example. Of these, lithium aluminum hydride, lithium borohydride, and sodium borohydride are preferred because of their excellent reduction rate and safety.

Moreover, it is preferable to add a reducing agent so that it may be a 1.5-10 times molar equivalent with respect to a metal ion. If the amount of the reducing agent added is within this range, the reducing action is sufficient, and the dispersion stability of the resulting metal-containing fine particles is also good, which is preferable.

On the other hand, the fine particle dispersion of this invention is a process of obtaining the aqueous solution containing a citrate ion and a ferric ion, and the aqueous solution contains gold, silver, platinum, palladium, tungsten, tantalum, bismuth, lead, indium, tin, titanium And adding an aqueous solution containing metal ions of at least one metal selected from the group consisting of aluminum while stirring to reduce the metal ions to obtain metal-containing fine particles, and to the liquid containing the metal-containing fine particles. You may manufacture by the manufacturing method provided with the process of producing the metal-containing microparticles | fine-particles which surface-coated with the dispersing agent by adding, stirring, the water-insoluble organic liquid which melt | dissolved the at least 2 sort (s) of dispersing agent from which the said vaporization temperature differs.

The conductive metal-containing material according to the fourth aspect of the present invention is the highest vaporization temperature and the lowest in the at least two kinds of dispersants after applying the fine particle dispersion according to the second aspect of the present invention to the coated object. It is a conductive metal containing material whose volume resistivity formed by baking at the temperature between vaporization temperatures is 60 microohm-cm or less, Preferably it is 40 microohm-cm or less, More preferably, 20 microohm-cm or less, Especially preferably, it is 10 microohm-cm or less.

In the present invention, the volume resistivity is a value calculated from a resistance value measured using a probe ohmmeter and a film thickness measured using a stylus type surface shape measuring instrument.

Here, as a method of apply | coating a microparticle dispersion liquid, a conventionally well-known method can be used. Specifically, for example, inkjet printing, screen printing, roll coater, air knife coater, blade coater, bar coater, gravure coater, die coater, spray coater, slide coater and the like. Among these, application | coating by inkjet printing is preferable because the correspondence to refinement | miniaturization and the change of a printing pattern are easy.

In the application by ink jet printing, the ink discharge hole is about 20 µm, and the ink droplet diameter changes in the space emergency after discharge, and reaches the adherend, after which it adheres to the adherend. It is preferable to widen into a phase. The diameter of the ink immediately after the ejection is about the ejection hole diameter, but changes to about 5 to 100 μm after the adherend is impacted. Therefore, when using the fine particle dispersion of this invention as ink, the aggregate of the microparticles | fine-particles in ink may be large, so long as it does not affect ink viscosity etc., and may be about 2 micrometers as an association aggregation diameter.

The to-be-coated object which apply | coats the said microparticle dispersion liquid is not specifically limited, As a specific example, resin substrates, such as a glass plate and an epoxy, etc. are mentioned.

Firing at the firing temperature means firing the fine particle dispersion coated on the coated object at the firing temperature set by the vaporization temperature of the dispersant to be used as described above. As a result, the metal-containing fine particles in the fine particle dispersion are fused to form a bulk body, and a conductive metal-containing material having a volume resistivity of 60 μΩcm or less is formed.

The reason why the volume resistivity of the conductive metal-containing material of the present invention is reduced is not clear in detail, but the inventors consider as follows.

First, when all vaporization temperatures of a single dispersing agent or a plurality of dispersing agents are higher than the firing temperature, the dispersing agent cannot be sufficiently dissociated from the surface of the metal-containing fine particles even by firing, and when the metal-containing fine particles are fused by firing, It is considered that the dispersant remains, inhibits the conductivity, and increases the volume resistivity. Secondly, when all the vaporization temperatures of a single dispersant or a plurality of dispersants are lower than the firing temperature, the dispersant is dissociated from the surface of the metal-containing fine particles by firing, which is preferable from the viewpoint of inhibiting conductivity. However, since the start of the fusion can only be expected by the effect of thermal vibration of the metal-containing fine particles, the fusion between the metal-containing fine particles is unlikely to proceed, so that the volume resistivity is considered to be high.

In contrast, in the present invention, a dispersant (first dispersant) which is surface-coated with a plurality of dispersants having a vaporization temperature associated with the firing temperature and has a large vaporization temperature, contributes to the dispersion stability near room temperature. Since it vaporizes before baking, it does not inhibit conduction. On the other hand, since the dispersing agent (second dispersing agent) in which a small amount exists in high vaporization temperature can approach metal microparticles | fine-particles by the effect of surface tension etc. on the surface of metal-containing microparticles | fine-particles, fusion between metal-containing microparticles | fine-particles can be promoted, volume resistivity It is thought that this was reduced. In addition, since the dispersing agent with a small vaporization temperature with a small amount exists hardly remain | survives after baking, it vaporizes (azeotropically) with the dispersing agent with a low vaporization temperature which exists in large quantities while making metal microparticles | proximity close. I think it is.

In order to further improve the conductivity of the conductive metal-containing material of the present invention, heating, ultraviolet irradiation, X-ray irradiation, electron beam irradiation, or the like may be further performed in addition to firing.

As heating, specifically, warm air heating, heat radiation, etc. are mentioned, for example.

As ultraviolet irradiation, specifically, the low pressure UV lamp which makes 254 nm main wavelength, the high pressure UV lamp which makes 365 nm main wavelength, etc. can be used, for example.

Hereinafter, the present invention will be described in more detail using examples. However, this invention is not limited to these Examples.

In addition, the vaporization temperature was measured by the following measurement conditions using the thermogravimetric analyzer (model: H-9000, Shimadzu Corporation make). The volume resistivity is determined from a resistance value measured using a probe ohmmeter (Model: Loresta IPMCP-T250, manufactured by Mitsubishi Oil Corporation), and a film thickness measured using a tactile surface shape measuring instrument (Model: Dektak6M, manufactured by veeco). Calculated.

[Measuring conditions]

Measuring start temperature: 25 ℃

Heating rate: 10 ℃ / min

Atmosphere: in nitrogen (flow rate: 20 mL / min)

Injection weight: 10mg

Cell used: aluminum (5 μL)

(Examples 1-1 to 1-9, Comparative Examples 1-11 to 1-19, Reference Examples 1-21 to 1-24: CuH colloid)

In a glass container, 5 g of copper (II) chloride hydrates were dissolved in 150 g of distilled water to obtain an aqueous solution. To this aqueous solution, 90 g of 40% aqueous citric acid solution (mass equivalent concentration, all the same below) was added, and a solution in which 0.08 g of dodecylamine and 0.02 g of methyloctadecylamine were dissolved in 10 g of xylene was further added. 150 g of 3% sodium borohydride aqueous solution was dripped slowly, stirring the solution after addition vigorously. After completion of the dropwise addition, the mixture was allowed to stand for 1 hour, separated into an aqueous layer and an oil layer, and only the oil layer was recovered to obtain a black fine particle dispersion in which the CuH colloid was dispersed.

The obtained fine particle dispersion was apply | coated to a glass plate, and after drying, the formed deposit was baked at 200 degreeC for 1 hour in nitrogen atmosphere, and the metal film of the gloss metallic copper color was formed. It was 5 micro-ohm-cm when the volume resistivity of this metal film was measured. In addition, the vaporization temperature of dodecylamine was 180 degreeC, and the vaporization temperature of methyloctadecylamine was 210 degreeC.

Similarly, the fine particle dispersion was prepared using the dispersing agent 1 instead of the dodecylamine, and the dispersing agent 2 instead of the methyloctadecylamine, baking for 1 hour at the predetermined | prescribed baking temperature, and forming a metal film and measuring the volume resistivity. . As a result, the dispersants 1 and 2 and the firing temperature are shown in Table 1-1 below. In addition, the example which uses one type of dispersing agent as a comparative example, and the example which uses two types of dispersing agent as a reference example but does not correspond to the Example in a 4th aspect from the relationship between vaporization temperature and baking temperature are implemented. In the same manner as in the example, the fine particle dispersion was prepared, and the volume resistivity of the metal film was measured. The results are shown in Tables 1-2 and 1-3 below. In addition, in following Table 1-2 and Table 1-3, "x" shows the inability to measure.

Example Dispersants 1
Vaporization temperature Dispersants 2
Vaporization temperature Firing temperature
[° C] Volume resistivity
[μΩcm] 1-1 Dodecylamine
180 ℃ Methyloctadecylamine
210 ℃ 200 ℃ 5 1-2 Tetradecylamine
190 ℃ Dimethyloctadecylamine
215 ℃ 200 ℃ 7 1-3 Hexadecylamine
200 ℃ Dimethyloctadecylamine
215 ℃ 210 ℃ 9 1-4 Dodecylamine
180 ℃ Octadecylamine
205 ℃ 200 ℃ 8 1-5 Dodecylamine
180 ℃ Dodecanosan
200 ℃ 190 ℃ 15 1-6 Dodecylamine
180 ℃ Dodecanethiol
205 ℃ 200 ℃ 7 1-7 Tetradecylamine
190 ℃ Dodecanosan
200 ℃ 195 ℃ 10 1-8 Dodecanosan
200 ℃ Tetradecanethiol
220 ℃ 210 ℃ 11 1-9 Hexadecylamine
200 ℃ Tetradecanethiol
220 ℃ 210 ℃ 9

Comparative example Dispersants 1
Vaporization temperature Dispersants 2
Vaporization temperature Firing temperature
[° C] Volume resistivity
[μΩcm] 1-11 Dodecylamine
180 ℃ - 200 ℃ × 1-12 Tetradecylamine
190 ℃ - 200 ℃ 500 1-13 Hexadecylamine
200 ℃ - 210 ℃ 750 1-14 Dodecanosan
200 ℃ - 210 ℃ 1000 1-15 Dodecylamine
180 ℃ - 150 ℃ 150 1-16 Tetradecylamine
190 ℃ - 180 DEG C 70 1-17 Hexadecylamine
200 ℃ - 180 DEG C 80 1-18 Dodecanosan
200 ℃ - 190 ℃ 110

Reference Example Dispersants 1
Vaporization temperature Dispersants 2
Vaporization temperature Firing temperature
[° C] Volume resistivity
[μΩcm] 1-21 Methyloctadecylamine
210 ℃ Dodecylamine
180 ℃ 220 ℃ × 1-22 Dimethyloctadecylamine
215 ℃ Tetradecylamine
190 ℃ 230 ℃ × 1-23 Hexadecylamine
200 ℃ Tetradecylamine
190 ℃ 180 DEG C 90 1-24 Dimethyloctadecylamine
215 ℃ Hexadecylamine
200 ℃ 190 ℃ 100

(Comparative Example 1-19)

A fine particle dispersion was prepared in the same manner as in Example 1-1 except that 0.1 g of propylamine (vaporization temperature: 40 ° C.) was used instead of 0.08 g of dodecylamine and 0.02 g of methyloctadecylamine. ?

The fine particle dispersions of Examples 1-1 to 1-9, Comparative Examples 1-11 to 1-19, and Reference Examples 1-21 to 1-24 prepared in this way were allowed to stand for 1 month under nitrogen-room temperature. As a result, the fine particle dispersions prepared in Examples 1-1 to 1-9, Comparative Examples 1-11 to 1-18, and Reference Examples 1-21 to 1-24 were black. On the other hand, in the fine particle dispersion prepared in Comparative Example 1-19, fine particles aggregated and precipitated, and the color of the supernatant liquid became transparent. Thereby, the fine particle dispersion prepared in Examples 1-1 to 1-9, Comparative Examples 1-11 to 1-18, and Reference Examples 1-21 to 1-24 assumes that the metal-containing fine particles are surface-coated with a dispersant. It was possible to confirm that it had excellent dispersion stability.

In addition, it is confirmed from the results shown in Tables 1-1, 1-2, and 1-3 that the fine particle dispersions prepared in Examples 1-1 to 1-9 can form metal films with low volume resistivity by firing. It was.

(Examples 2-1 to 2-9, Comparative Examples 2-11 to 2-19, Reference Examples 2-21 to 2-24: Ag colloid)

In a glass container, 14 g of sodium citrate dihydrate and 10 g of iron (II) sulfide heptahydrate were dissolved in 60 g of distilled water to obtain an aqueous solution. To this aqueous solution, 25 g of a 10% silver nitrate aqueous solution (mass equivalent concentration, all the same below) was added, and the resulting precipitate was centrifuged and dispersed in 1 kg of distilled water. Next, the solution which melt | dissolved 0.04 g of dodecylamine and 0.01 g of methyloctadecylamine in 2.5 g of cyclohexanes was added to this solution, and it stirred for 1 hour. While the solution after the addition was stirred, 2.5 g of sodium chloride was further added. Thereafter, the mixture was left to stand for 1 hour and separated into an aqueous layer and an oil layer, and only the oil layer was recovered to obtain a black fine particle dispersion in which Ag colloid was dispersed.

After the obtained fine particle dispersion was apply | coated to a glass plate and dried, the formed deposit was baked at 200 degreeC in nitrogen atmosphere for 1 hour, and the shiny metallic silver metal film was formed. It was 5 micro-ohm-cm when the volume resistivity of this metal film was measured.

Similarly, the fine particle dispersion was prepared using dispersant 1 instead of dodecylamine and dispersant 2 instead of methyloctadecylamine, and calcined at a predetermined firing temperature for 1 hour to form a metal film to measure volume resistivity. . As a result, the dispersants 1 and 2 and the firing temperature are shown in Table 2-1 below. In addition, the example which uses one type of dispersing agent as a comparative example, and the example which uses two types of dispersing agent as a reference example but does not correspond to the Example in a 4th aspect from the relationship between vaporization temperature and baking temperature are implemented. In the same manner as in the example, the fine particle dispersion was prepared, and the volume resistivity of the metal film was measured. The results are shown in Tables 2-2 and 2-3 below. In addition, in following Table 2-2 and Table 2-3, "x" shows the inability to measure.

Example Dispersants 1
Vaporization temperature Dispersants 2
Vaporization temperature Firing temperature
[° C] Volume resistivity
[μΩcm] 2-1 Dodecylamine
180 ℃ Methyloctadecylamine
210 ℃ 200 ℃ 5 2-2 Tetradecylamine
190 ℃ Dimethyloctadecylamine
215 ℃ 200 ℃ 9 2-3 Hexadecylamine
200 ℃ Dimethyloctadecylamine
215 ℃ 210 ℃ 4 2-4 Dodecylamine
180 ℃ Octadecylamine
205 ℃ 200 ℃ 7 2-5 Dodecylamine
180 ℃ Dodecanosan
200 ℃ 190 ℃ 11 2-6 Dodecylamine
180 ℃ Dodecanethiol
205 ℃ 200 ℃ 5 2-7 Tetradecylamine
190 ℃ Dodecanosan
200 ℃ 195 ℃ 10 2-8 Dodecanosan
200 ℃ Tetradecanethiol
220 ℃ 210 ℃ 6 2-9 Hexadecylamine
200 ℃ Tetradecanethiol
220 ℃ 210 ℃ 9

Comparative example Dispersants 1
Vaporization temperature Dispersants 2
Vaporization temperature Firing temperature
[° C] Volume resistivity
[μΩcm] 2-11 Dodecylamine
180 ℃ - 200 ℃ × 2-12 Tetradecylamine
190 ℃ - 200 ℃ × 2-13 Hexadecylamine
200 ℃ - 210 ℃ 1000 2-14 Dodecanosan
200 ℃ - 210 ℃ × 2-15 Dodecylamine
180 ℃ - 150 ℃ 250 2-16 Tetradecylamine
190 ℃ - 180 DEG C 65 2-17 Hexadecylamine
200 ℃ - 180 DEG C 80 2-18 Dodecanosan
200 ℃ - 190 ℃ 130

Reference Example Dispersants 1
Vaporization temperature Dispersants 2
Vaporization temperature Firing temperature
[° C] Volume resistivity
[μΩcm] 2-21 Methyloctadecylamine
210 ℃ Dodecylamine
180 ℃ 220 ℃ × 2-22 Dimethyloctadecylamine
215 ℃ Tetradecylamine
190 ℃ 230 ℃ × 2-23 Hexadecylamine
200 ℃ Tetradecylamine
190 ℃ 180 DEG C 90 2-24 Dimethyloctadecylamine
215 ℃ Hexadecylamine
200 ℃ 190 ℃ 120

(Comparative Example 2-19)

A fine particle dispersion was prepared in the same manner as in Example 2-1, except that 0.05 g of propylamine was used instead of 0.04 g of dodecylamine and 0.01 g of methyloctadecylamine.

The fine particle dispersions of Examples 2-1 to 2-9, Comparative Examples 2-11 to 2-19, and Reference Examples 2-21 to 2-24 prepared in this way were allowed to stand for 1 month under nitrogen-room temperature. As a result, the fine particle dispersion prepared in Examples 2-1 to 2-9, Comparative Examples 2-11 to 2-18, and Reference Examples 2-21 to 2-24 was black. On the other hand, in the fine particle dispersion prepared in Comparative Example 2-19, fine particles aggregated and precipitated, and the color of the supernatant liquid became transparent. Thereby, the fine particle dispersion prepared in Examples 2-1 to 2-9, Comparative Examples 2-11 to 2-18, and Reference Examples 2-21 to 2-24 assumes that the metal-containing fine particles are surface-coated with a dispersant. It was able to confirm that it had excellent dispersion stability.

In addition, from the results shown in Tables 2-1, 2-2, and 2-3, it was confirmed that the fine particle dispersions prepared in Examples 2-1 to 2-9 can form metal films with low volume resistivity by firing. It was.

(Examples 3-1 to 3-9, Comparative Examples 3-11 to 3-19, Reference Examples 3-21 to 3-24: Au colloid)

In a glass container, 1.5 g of gold (III) chloride acids were dissolved in 150 g of distilled water to obtain an aqueous solution. 3g (mass conversion concentration, all the same below) of 1% citric acid aqueous solution was added, heating this boiling aqueous solution. After 90 seconds, the liquid color turned red. Next, to 150 g of this solution, a solution in which 0.04 g of dodecylamine and 0.01 g of methyloctadecylamine were dissolved in 5 g of n-octane was added, followed by stirring for 1 hour. While the solution after the addition was stirred, 2.5 g of sodium chloride was further added. Thereafter, the mixture was left to stand for 1 hour and separated into an aqueous layer and an oil layer, and only the oil layer was recovered to obtain a black red fine particle dispersion in which Au colloid was dispersed.

After the obtained fine particle dispersion was apply | coated to a glass plate and dried, the formed deposit was baked at 200 degreeC for 1 hour in nitrogen atmosphere, and the shiny metallic gold metal film was formed. It was 6 micro-ohm cm when the volume resistivity of this metal film was measured.

Similarly, the fine particle dispersion was prepared using the dispersing agent 1 instead of the dodecylamine, and the dispersing agent 2 instead of the methyloctadecylamine, baking for 1 hour at the predetermined | prescribed baking temperature, and forming a metal film and measuring the volume resistivity. . As a result, the dispersants 1 and 2 and the firing temperature are shown in Table 3-1 below. In addition, the example which uses one type of dispersing agent as a comparative example, and the example which uses two types of dispersing agent as a reference example but does not correspond to the Example in a 4th aspect from the relationship between vaporization temperature and baking temperature are implemented. In the same manner as in the example, the fine particle dispersion was prepared, and the volume resistivity of the metal film was measured. The results are shown in Tables 3-2 and 3-3 below. In addition, in the following Table 3-2 and Table 3-3, "x" represents the inability to measure.

Example Dispersants 1
Vaporization temperature Dispersants 2
Vaporization temperature Firing temperature
[° C] Volume resistivity
[μΩcm] 3-1 Dodecylamine
180 ℃ Methyloctadecylamine
210 ℃ 200 ℃ 6 3-2 Tetradecylamine
190 ℃ Dimethyloctadecylamine
215 ℃ 200 ℃ 8 3-3 Hexadecylamine
200 ℃ Dimethyloctadecylamine
215 ℃ 210 ℃ 4 3-4 Dodecylamine
180 ℃ Octadecylamine
205 ℃ 200 ℃ 8 3-5 Dodecylamine
180 ℃ Dodecanosan
200 ℃ 190 ℃ 18 3-6 Dodecylamine
180 ℃ Dodecanethiol
205 ℃ 200 ℃ 6 3-7 Tetradecylamine
190 ℃ Dodecanosan
200 ℃ 195 ℃ 11 3-8 Dodecanosan
200 ℃ Tetradecanethiol
220 ℃ 210 ℃ 5 3-9 Hexadecylamine
200 ℃ Tetradecanethiol
220 ℃ 210 ℃ 9

Comparative example Dispersants 1
Vaporization temperature Dispersants 2
Vaporization temperature Firing temperature
[° C] Volume resistivity
[μΩcm] 3-11 Dodecylamine
180 ℃ - 200 ℃ 650 3-12 Tetradecylamine
190 ℃ - 200 ℃ × 3-13 Hexadecylamine
200 ℃ - 210 ℃ × 3-14 Dodecanosan
200 ℃ - 210 ℃ × 3-15 Dodecylamine
180 ℃ - 150 ℃ 550 3-16 Tetradecylamine
190 ℃ - 180 DEG C 170 3-17 Hexadecylamine
200 ℃ - 180 DEG C 210 3-18 Dodecanosan
200 ℃ - 190 ℃ 350

Reference Example Dispersants 1
Vaporization temperature Dispersants 2
Vaporization temperature Firing temperature
[° C] Volume resistivity
[μΩcm] 3-21 Methyloctadecylamine
210 ℃ Dodecylamine
180 ℃ 220 ℃ 800 3-22 Dimethyloctadecylamine
215 ℃ Tetradecylamine
190 ℃ 230 ℃ × 3-23 Hexadecylamine
200 ℃ Tetradecylamine
190 ℃ 180 DEG C 110 3-24 Dimethyloctadecylamine
215 ℃ Hexadecylamine
200 ℃ 190 ℃ 230

(Comparative Example 3-19)

A fine particle dispersion was prepared in the same manner as in Example 3-1, except that 0.05 g of propylamine was used instead of 0.04 g of dodecylamine and 0.01 g of methyloctadecylamine.

The fine particle dispersions of Examples 3-1 to 3-9, Comparative Examples 3-11 to 3-19, and Reference Examples 3-21 to 3-24 prepared in this way were allowed to stand for 1 month under nitrogen-room temperature. As a result, the fine particle dispersion prepared in Examples 3-1 to 3-9, Comparative Examples 3-11 to 3-18, and Reference Examples 3-21 to 3-24 was black. On the other hand, in the fine particle dispersion prepared in Comparative Example 3-19, fine particles aggregated and precipitated, and the color of the supernatant liquid became transparent. Thereby, in the fine particle dispersion prepared in Examples 3-1 to 3-9, Comparative Examples 3-11 to 3-18, and Reference Examples 3-21 to 3-24, it is assumed that metal-containing fine particles are surface-coated with a dispersant. It was able to confirm that it had excellent dispersion stability.

From the results shown in Tables 3-1, 3-2, and 3-3, it was confirmed that the fine particle dispersions prepared in Examples 3-1 to 3-9 can form metal films with low volume resistivity by firing. It was.

(Examples 4-1 to 4-9, Comparative Examples 4-11 to 4-19, Reference Examples 4-21 to 4-24: Ni colloid)

In a glass container, 5 g of nickel chloride (II) dihydrate was dissolved in 150 g of distilled water to obtain an aqueous solution. To this aqueous solution, 90 g of a 40% citric acid aqueous solution (mass equivalent concentration, all the same below) was added, and a solution in which 0.08 g of dodecylamine and 0.02 g of methyloctadecylamine were dissolved in 10 g of n-hexane was further added. 150 g of 3% sodium borohydride aqueous solution was dripped slowly, stirring the solution after addition vigorously. After completion of the dropwise addition, the mixture was allowed to stand for 1 hour, separated into an aqueous layer and an oil layer, and only the oil layer was recovered to obtain a black fine particle dispersion in which Ni colloid was dispersed.

The obtained fine particle dispersion was apply | coated to a glass plate, and after drying, the formed deposit was baked at 200 degreeC in nitrogen atmosphere for 1 hour, and the gray metal film was formed. The volume resistivity of this metal film was measured, and found to be 23 μΩcm.

Similarly, the fine particle dispersion was prepared using the dispersing agent 1 instead of the dodecylamine, and the dispersing agent 2 instead of the methyloctadecylamine, baking for 1 hour at the predetermined | prescribed baking temperature, and forming a metal film and measuring the volume resistivity. . As a result, the dispersants 1 and 2 and the firing temperature are shown in Table 4-1 below. In addition, the example which uses one type of dispersing agent as a comparative example, and the example which uses two types of dispersing agent as a reference example but does not correspond to the Example in a 4th aspect from the relationship between vaporization temperature and baking temperature are implemented. In the same manner as in the example, the fine particle dispersion was prepared, and the volume resistivity of the metal film was measured. The results are shown in Tables 4-2 and 4-3 below. In addition, in the following Table 4-2 and Table 4-3, "x" represents the inability to measure.

Example Dispersants 1
Vaporization temperature Dispersants 2
Vaporization temperature Firing temperature
[° C] Volume resistivity
[μΩcm] 4-1 Dodecylamine
180 ℃ Methyloctadecylamine
210 ℃ 200 ℃ 23 4-2 Tetradecylamine
190 ℃ Dimethyloctadecylamine
215 ℃ 200 ℃ 30 4-3 Hexadecylamine
200 ℃ Dimethyloctadecylamine
215 ℃ 210 ℃ 29 4-4 Dodecylamine
180 ℃ Octadecylamine
205 ℃ 200 ℃ 35 4-5 Dodecylamine
180 ℃ Dodecanosan
200 ℃ 190 ℃ 22 4-6 Dodecylamine
180 ℃ Dodecanethiol
205 ℃ 200 ℃ 27 4-7 Tetradecylamine
190 ℃ Dodecanosan
200 ℃ 195 ℃ 24 4-8 Dodecanosan
200 ℃ Tetradecanethiol
220 ℃ 210 ℃ 31 4-9 Hexadecylamine
200 ℃ Tetradecanethiol
220 ℃ 210 ℃ 29

Comparative example Dispersants 1
Vaporization temperature Dispersants 2
Vaporization temperature Firing temperature
[° C] Volume resistivity
[μΩcm] 4-11 Dodecylamine
180 ℃ - 200 ℃ × 4-12 Tetradecylamine
190 ℃ - 200 ℃ 350 4-13 Hexadecylamine
200 ℃ - 210 ℃ × 4-14 Dodecanosan
200 ℃ - 210 ℃ 1500 4-15 Dodecylamine
180 ℃ - 150 ℃ 1500 4-16 Tetradecylamine
190 ℃ - 180 DEG C 530 4-17 Hexadecylamine
200 ℃ - 180 DEG C 780 4-18 Dodecanosan
200 ℃ - 190 ℃ 820

Reference Example Dispersants 1
Vaporization temperature Dispersants 2
Vaporization temperature Firing temperature
[° C] Volume resistivity
[μΩcm] 4-21 Methyloctadecylamine
210 ℃ Dodecylamine
180 ℃ 220 ℃ × 4-22 Dimethyloctadecylamine
215 ℃ Tetradecylamine
190 ℃ 230 ℃ 580 4-23 Hexadecylamine
200 ℃ Tetradecylamine
190 ℃ 180 DEG C 680 4-24 Dimethyloctadecylamine
215 ℃ Hexadecylamine
200 ℃ 190 ℃ 800

(Comparative Example 4-19)

A fine particle dispersion was prepared in the same manner as in Example 4-1, except that 0.1 g of propylamine (vaporization temperature: 40 ° C) was used instead of 0.08 g of dodecylamine and 0.02 g of methyloctadecylamine.

The fine particle dispersions of Examples 4-1 to 4-9, Comparative Examples 4-11 to 4-19, and Reference Examples 4-21 to 4-24 prepared in this way were allowed to stand for 1 month under nitrogen-room temperature. As a result, the fine particle dispersion prepared in Examples 4-1 to 4-9, Comparative Examples 4-11 to 4-18, and Reference Examples 4-21 to 4-24 was black. On the other hand, in the fine particle dispersion prepared in Comparative Example 4-19, the fine particles caused aggregation and precipitated, and the color of the supernatant liquid became transparent. Thereby, in the fine particle dispersion prepared in Examples 4-1 to 4-9, Comparative Examples 4-11 to 4-18, and Reference Examples 4-21 to 4-24, it is assumed that metal-containing fine particles are surface-coated with a dispersant. It was able to confirm that it had excellent dispersion stability.

In addition, from the results shown in Tables 4-1, 4-2, and 4-3, it was confirmed that the fine particle dispersions prepared in Examples 4-1 to 4-9 can form metal films with low volume resistivity by firing. It was.

(Examples 5-1 to 5-9, Comparative Examples 5-11 to 5-19, Reference Examples 5-21 to 5-24: CuH colloid)

In a glass container, 5 g of copper (II) chloride hydrates were dissolved in 150 g of distilled water to obtain an aqueous solution. To this aqueous solution, 90 g of 40% citric acid aqueous solution (mass equivalent concentration, all the same below) was added, and a solution in which 0.08 g of dodecylamine and 0.02 g of methyloctadecylamine were dissolved in 10 g of toluene was further added. 150 g of 3% sodium borohydride aqueous solution was dripped slowly, stirring the solution after addition vigorously. After completion of the dropwise addition, the mixture was allowed to stand for 1 hour, separated into an aqueous layer and an oil layer, and only the oil layer was recovered to obtain a black fine particle dispersion in which the CuH colloid was dispersed.

10 g of AF solvents (manufactured by Nippon Petroleum Co., Ltd.) was added to the obtained fine particle dispersion, and toluene was evaporated by performing a reduced pressure using a vacuum pump at room temperature to carry out solvent substitution.

The fine particle dispersion using AF solvent thus obtained as a dispersion medium was applied to the glass plate and dried, and then the formed deposit was fired at 200 ° C. for 1 hour in a nitrogen atmosphere. As a result, a shiny metallic copper colored metal film was formed. It was 7 micro-ohm-cm when the volume resistivity of this metal film was measured.

Similarly, the fine particle dispersion was prepared using dispersant 1 instead of dodecylamine and dispersant 2 instead of methyloctadecylamine, and calcined at a predetermined firing temperature for 1 hour to form a metal film to measure volume resistivity. . As a result, the dispersants 1 and 2 and the firing temperature are shown in Table 5-1 below. In addition, the example which uses one type of dispersing agent as a comparative example, and the example which uses two types of dispersing agent as a reference example but does not correspond to the Example in a 4th aspect from the relationship between vaporization temperature and baking temperature are implemented. In the same manner as in the example, the fine particle dispersion was prepared, and the volume resistivity of the metal film was measured. The results are shown in Tables 5-2 and 5-3 below. In addition, in following Table 5-2 and Table 5-3, "x" shows the inability to measure.

Example Dispersants 1
Vaporization temperature Dispersants 2
Vaporization temperature Firing temperature
[° C] Volume resistivity
[μΩcm] 5-1 Dodecylamine
180 ℃ Methyloctadecylamine
210 ℃ 200 ℃ 8 5-2 Tetradecylamine
190 ℃ Dimethyloctadecylamine
215 ℃ 200 ℃ 7 5-3 Hexadecylamine
200 ℃ Dimethyloctadecylamine
215 ℃ 210 ℃ 8 5-4 Dodecylamine
180 ℃ Octadecylamine
205 ℃ 200 ℃ 9 5-5 Dodecylamine
180 ℃ Dodecanosan
200 ℃ 190 ℃ 11 5-6 Dodecylamine
180 ℃ Dodecanethiol
205 ℃ 200 ℃ 11 5-7 Tetradecylamine
190 ℃ Dodecanosan
200 ℃ 195 ℃ 9 5-8 Dodecanosan
200 ℃ Tetradecanethiol
220 ℃ 210 ℃ 11 5-9 Hexadecylamine
200 ℃ Tetradecanethiol
220 ℃ 210 ℃ 13

Comparative example Dispersants 1
Vaporization temperature Dispersants 2
Vaporization temperature Firing temperature
[° C] Volume resistivity
[μΩcm] 5-11 Dodecylamine
180 ℃ - 200 ℃ × 5-12 Tetradecylamine
190 ℃ - 200 ℃ 400 5-13 Hexadecylamine
200 ℃ - 210 ℃ 650 5-14 Dodecanosan
200 ℃ 210 ℃ 900 5-15 Dodecylamine
180 ℃ - 150 ℃ 140 5-16 Tetradecylamine
190 ℃ - 180 DEG C 90 5-17 Hexadecylamine
200 ℃ - 180 DEG C 100 5-18 Dodecanosan
200 ℃ - 190 ℃ 110

Reference Example Dispersants 1
Vaporization temperature Dispersants 2
Vaporization temperature Firing temperature
[° C] Volume resistivity
[μΩcm] 5-21 Methyloctadecylamine
210 ℃ Dodecylamine
180 ℃ 220 ℃ × 5-22 Dimethyloctadecylamine
215 ℃ Tetradecylamine
190 ℃ 230 ℃ × 5-23 Hexadecylamine
200 ℃ Tetradecylamine
190 ℃ 180 DEG C 110 5-24 Dimethyloctadecylamine
215 ℃ Hexadecylamine
200 ℃ 190 ℃ 120

(Comparative Example 5-19)

A fine particle dispersion was prepared in the same manner as in Example 5-1, except that 0.1 g of propylamine was used instead of 0.08 g of dodecylamine and 0.02 g of methyloctadecylamine.

The fine particle dispersions of Examples 5-1 to 5-9, Comparative Examples 5-11 to 5-19, and Reference Examples 5-21 to 5-24 prepared in this way were allowed to stand for 1 month under nitrogen-room temperature. As a result, the fine particle dispersion prepared in Examples 5-1 to 5-9, Comparative Examples 5-11 to 5-18, and Reference Examples 5-21 to 5-24 was black. On the other hand, in the fine particle dispersion prepared in Comparative Example 5-19, fine particles aggregated and precipitated, and the color of the supernatant liquid became transparent. Thereby, the fine particle dispersion prepared in Examples 5-1 to 5-9, Comparative Examples 5-11 to 5-18, and Reference Examples 5-21 to 5-24 assumes that the metal-containing fine particles are surface-coated with a dispersant. It was able to confirm that it had excellent dispersion stability.

From the results shown in Table 5-1 above, it was confirmed that the fine particle dispersions prepared in Examples 5-1 to 5-9 can form metal films with low volume resistivity by firing.

As can be seen from the results shown in Tables 1 to 5, metal-containing fine particles (CuH colloid, Ag colloid, Au colloid, Ni colloid) coated with a dispersant vaporized below the firing temperature and a dispersant vaporized above the firing temperature It was found that the volume resistivity of the metal film formed by using the dispersed fine particle dispersion was remarkably low.

In addition, the contents of the full specification of Japanese Patent Application No. 2004-68065 (filed with the Japan Patent Office on March 10, 2004), which are the basis for claiming priority of the present application, are cited herein, and are introduced as the disclosure of the specification of the present invention. It is.

Claims (6)

As metal-containing microparticles | fine-particles surface-coated by the at least 2 sort (s) of dispersing agent from which vaporization temperature differs, The said microparticles | fine-particles consist only of microparticles | fine-particles whose average particle diameter of the said microparticles are 1-100 nm, are disperse | distributed to the microparticle dispersion liquid used for baking at the temperature of the baking of 150-210 degreeC, Metal-containing fine particles, which are surface-coated with a dispersant vaporized below the firing temperature and a dispersant vaporized above the firing temperature. delete The fine particle dispersion liquid of the metal containing fine particle of Claim 1 is disperse | distributed in the water-insoluble organic liquid. As a manufacturing method of manufacturing the fine particle dispersion of Claim 3, Adding water to a water-soluble metal-containing compound to obtain an aqueous solution containing metal ions, Adding a water-insoluble organic liquid in which at least two kinds of dispersants having different vaporization temperatures are dissolved into the aqueous solution; After the addition of the organic liquid, a method of producing a fine particle dispersion comprising the step of reducing the metal ions by producing a metal-containing fine particle surface-coated with at least two kinds of dispersants having different vaporization temperatures by adding a reducing agent with stirring. . As a manufacturing method of manufacturing the fine particle dispersion of Claim 3, Obtaining an aqueous solution containing citrate ions and ferric ions, By adding while stirring the aqueous solution containing the ion of 1 or more types of metals chosen from the group which consists of gold, silver, platinum, palladium, tungsten, tantalum, bismuth, lead, indium, tin, titanium, and aluminum, Reducing the metal ions to obtain metal-containing fine particles; The metal containing surface-coated with the at least 2 type of dispersing agent from which the vaporization temperature differs by adding to the liquid containing the said metal containing microparticles, stirring, the water-insoluble organic liquid which melt | dissolved the at least 2 type of dispersing agent from which the said vaporization temperature differs, stirring. A method for producing a particulate dispersion comprising a step of producing particulates. A conductive metal-containing material having a volume resistivity of 60 μΩcm or less formed by applying the fine particle dispersion according to claim 3 to the object to be coated and then baking at a temperature between the highest and lowest vaporization temperatures of the at least two dispersants. .