JP3933138B2 - Inkjet metal ink - Google Patents

Description

  The present invention relates to a metal ink for ink jet suitable for forming a fine conductor wiring, a thin conductive film having a uniform thickness, and the like by an ink jet printing method.

  As a material for forming a conductor wiring, a conductive film or the like, very fine metal fine particles having a particle diameter of about several nm to several tens of nm are used. Specifically, in order to prevent such agglomeration of particles and improve dispersibility, a metal colloid solution dispersed in a dispersion medium in the presence of a dispersant is used as an ink for various printing methods and coating methods. As described above, a conductor wiring or a conductive film is formed by printing or coating on a base material and then baking as necessary.

  Recently, an ink jet printing method using an ink jet printer has attracted attention as a method for forming a conductor wiring or a conductive film, and the use of a metal colloid solution as a metal ink for the ink jet printing method has been studied. However, conventional metal colloidal solutions are generally water-based using water as a dispersion medium, and their physical properties such as viscosity, surface tension, and vapor pressure (boiling point) are only in a limited range.

Therefore, it has been studied to impart physical properties suitable for ink jet metal ink to a metal colloid solution. As physical properties required for ink-jet metal ink,
・ The dispersed fine metal particles do not settle easily.
・ The particle size of the metal fine particles is uniform, and moreover, a plurality of metal fine particles are aggregated to make it difficult to produce secondary particles with a large particle size, and the ink viscosity is low. Not happen,
-In the case of ink for piezo-type ink jet printing method using a piezo element, the vapor pressure is low and the viscosity does not easily rise or dry.
-In the case of ink for ink jet printing using a so-called thermal method using a heating element, conversely, the vapor pressure is high and bubbles are likely to be generated due to the heat generated by the heating element.
Etc.

In order to adjust the physical properties of the metal ink for ink jet made of a metal colloid solution, it has been studied to use not only water but also various organic solvents as a dispersion medium that directly affects the physical properties. For example, in Patent Document 1, it is known that metal fine particles having a uniform particle diameter can be produced, so that metal ions are reduced by reducing metal ions in water in the presence of a dispersant by a so-called liquid phase reduction method. Applying the method of producing an aqueous metal colloid solution by precipitating,
・ A metal colloid solution in which the dispersion medium is an organic solvent is produced by dissolving a metal compound that is a source of metal ions in an organic solvent, adding a dispersant, and then reducing and precipitating metal fine particles. Method,
-Dissolve the metal compound that is the source of metal ions in water, add a water-soluble organic solvent and a dispersing agent, and then reduce it to precipitate metal fine particles. A method for producing a metal colloid solution which is a mixed solvent with an organic solvent,
Is described.

Further, Patent Document 2 applies a method of producing metal fine particles by a vapor phase growth method so that vapor of a high-boiling organic solvent such as mineral spirit is brought into contact with metal fine particles that are being grown in the gas phase. In addition, a method for producing a metal colloid solution (independent dispersion) in which metal fine particles are dispersed in an organic solvent by cooling and collecting the metal fine particles is described.
JP-A-11-80647 (claims 11, 12, column 0042, column 0045 to column 0046) JP 2001-35255 A (column 0006)

  However, among the methods described in Patent Document 1, in the method using an organic solvent as a dispersion medium, the metal compound having excellent solubility in a specific organic solvent and the types of reducing agents are limited. There is a problem that the kind of is limited.

  Moreover, in the method using a mixed solvent of water and a water-soluble organic solvent, a widely used water-soluble metal compound or reducing agent can be used, but many of these are soluble in water-soluble organic solvents. Therefore, when the water-soluble organic solvent is added, a part of the water-soluble organic solvent is precipitated, and the concentration of the reaction system is likely to be uneven.

  As a result of variations in the particle size of the formed metal fine particles due to the unevenness of the concentration, when this metal colloid solution is used as a metal ink for ink jet, clogging is caused by nozzles of an ink jet printer. It tends to occur. In addition, the structure and conductivity of the formed conductor wiring and conductive film may be non-uniform. Further, the unreacted metal compound may be mixed into the metal fine particles as impurities, and the metal fine particles, and thus the conductivity of the conductor wiring or the conductive film may be hindered.

  In addition, the method described in Patent Document 2 can be applied only to a high-boiling organic solvent that needs to be handled with care in terms of safety and environment, and has a problem that the application range is narrow. In addition, an organic solvent such as mineral spirit may dissolve an adhesive used in an inkjet printer head or the like.

  The present invention includes a water-based dispersion medium that is easy to handle in terms of safety and environment, and metal fine particles having a uniform particle size and excellent conductivity, and has physical properties suitable for an inkjet printing method. The object is to provide a metal ink for inkjet.

The invention described in claim 1 includes metal fine particles having a primary particle size of 200 nm or less deposited by reducing metal ions in water, a dispersant having a molecular weight of 200 to 30000, water as a dispersion medium, look containing a mixed solvent of a water-soluble organic solvent, and the water-soluble organic solvent, alcohols, ketones, glycol ethers, and with at least one selected from the group consisting of nitrogen-containing organic compounds in water-soluble, A metal ink for ink-jet recording, wherein the proportion of the water-soluble organic solvent in the mixed solvent is 75% by weight or more .

The invention according to claim 2 is used for piezo ink jet printing, has a surface tension of 30 to 45 mN / m (25 ° C.), a viscosity of 0.5 to 19 mPa · s (25 ° C.) , and a boiling point of 100 ° C. The metal ink for ink jet according to claim 1, which is as described above.

  The invention according to claim 3 includes a step of completely separating metal fine particles from water using an aqueous metal colloid solution obtained by reducing metal ions in water and precipitating metal fine particles as a starting material. The metal ink for ink jet according to claim 1, wherein the ink is manufactured without going through.

  In the metal ink for ink-jet according to the first aspect of the present invention, since the metal fine particles having a uniform particle diameter produced by a liquid phase reduction method using water are used, the nozzles of the ink-jet printer It is possible to prevent clogging from occurring. In addition, it is possible to prevent the structure, conductivity, and the like of the formed conductor wiring and conductive film from being varied, and to improve the uniformity. In addition, since the metal fine particles contain almost no impurities such as unreacted metal compounds and are excellent in conductivity, the conductivity of the conductor wiring and the conductive film can be improved.

Further, since a mixed solvent of water and a water-soluble organic solvent is used as the dispersion medium, handling is easy in terms of safety and environment. Moreover, as the water-soluble organic solvent, at least one selected from the group consisting of alcohols, ketones, glycol ethers, and water-soluble nitrogen-containing organic compounds is selected, and the water-soluble organic solvent occupies the mixed solvent. By limiting the ratio to 75% by weight or more, physical properties such as viscosity, surface tension, and vapor pressure of the metal ink for ink jet can be easily adjusted within a range suitable for the ink jet printing method.

According to the invention of claim 2, the surface tension is adjusted to 30 to 45 mN / m (25 ° C.), the viscosity is adjusted to 0.5 to 19 mPa · s (25 ° C.) , and the boiling point is adjusted to a range of 100 ° C. or more. Therefore, without causing clogging at the nozzles or other discharge defects, the ink can be discharged well from the nozzles by the piezo ink jet printing method, and the conductor wiring or conductive film Can be formed.

  According to the invention of claim 3, without using a water-based metal colloid solution obtained by a reduction precipitation method as a starting material, without passing through a step of completely separating metal fine particles from water, Metallic ink for ink-jet is manufactured without generating secondary particles due to agglomeration caused by complete separation from water, variation in the particle size that accompanies it, and increase in overall particle size. The For this reason, the manufactured ink-jet metal ink maintains a state in which the metal fine particles are uniformly dispersed in the dispersion medium immediately after being produced by the reduction precipitation method, almost in the form of primary particles, By using such metal ink jet ink, it is possible to more reliably prevent clogging from occurring in the nozzle of the ink jet printer. Further, the structure and conductivity of the conductor wiring and the conductive film can be further uniformized.

The present invention is described below.
The ink-jet metal ink of the present invention comprises metal fine particles having a primary particle size of 200 nm or less, precipitated by reducing metal ions in water, a dispersant having a molecular weight of 200 to 30000, and water as a dispersion medium. look containing a mixed solvent of a water-soluble organic solvent and, and the water-soluble organic solvent, alcohols, ketones, glycol ethers, and with at least one selected from the group consisting of nitrogen-containing organic compounds in water-soluble The ratio of the water-soluble organic solvent in the mixed solvent is 75% by weight or more .

  Among these, the primary particle diameter of the metal fine particles is limited to 200 nm or less for the following reason. That is, large metal fine particles having a primary particle size exceeding 200 nm have low dispersibility in the metal ink for ink jet, and tend to aggregate to produce secondary particles. Moreover, even if it does not aggregate, the fluidity | liquidity of the metal ink for inkjets is reduced. For this reason, the ink-jet metal ink containing such large metal fine particles can not only satisfy the physical properties for the ink-jet printing method but also easily causes clogging of the nozzle. In addition, the conductor wiring and the conductive film formed using the ink jet metal ink are not uniform in structure and conductivity due to generation of secondary particles.

On the other hand, very fine metal fine particles having a primary particle size of 200 nm or less are excellent in dispersibility in the metal ink for ink-jet, and thus hardly cause aggregation. In addition, the fluidity of the metal ink for ink jet is improved. Therefore, as described above, the ink-jet metal ink of the present invention containing metal fine particles having a primary particle size of 200 nm or less includes alcohol, ketone, glycol ether, and water-soluble nitrogen-containing organic as a water-soluble organic solvent. By selecting at least one selected from the group consisting of compounds and limiting the proportion of the water-soluble organic solvent in the mixed solvent of water and the water-soluble organic solvent to 75% by weight or more, for an inkjet printing method optimal properties as, i.e. viscosity, surface tension, and on the scope of the vapor pressure can be fully satisfied, it is possible to occur difficulty Kusuru clogging of the nozzle. In addition, the conductor wiring and conductive film formed using the inkjet metal ink of the present invention have extremely uniform structure and conductivity.

  The lower limit value of the primary particle size of the metal fine particles is not particularly limited, and theoretically, the metal particles can be used up to the smallest particle size that can have conductivity as a metal, but in practical use. It is preferably 1 nm or more. That is, the primary particle size of the metal fine particles is preferably 1 to 200 nm.

  The blending ratio of the metal fine particles is preferably 0.1 to 90% by weight in the total amount of the metal ink for inkjet. If the blending ratio is less than 0.1% by weight, the metal ink for ink jet is too thin, and there is a possibility that a conductor wiring or conductive film having sufficient thickness and conductivity cannot be formed by the ink jet printing method. On the other hand, when it exceeds 90% by weight, the fluidity is lowered, and there is a possibility that an ink suitable for an inkjet printing method cannot be obtained.

  The primary particle size and blending ratio of the metal fine particles have optimum physical properties suitable for various ink-jet printing methods employed when forming a conductor wiring or a conductive film using the ink-jet metal ink of the present invention. It is preferable to select a more suitable range suitable for each inkjet printing method from the above range. As the metal fine particles, those made of various metals and alloys can be used. In particular, in consideration of imparting good conductivity to the conductor wiring and the conductive film, nickel, copper, silver, gold, platinum, Fine particles made of palladium or an alloy thereof are preferable.

  As the dispersant, those having a molecular weight of 200 to 30,000 are used from various dispersants having good solubility in water or a water-soluble organic solvent. This is because when the molecular weight of the dispersant is less than 200, the effect of stably dispersing the metal fine particles cannot be obtained. On the other hand, when the molecular weight exceeds 30000, the effect of stably dispersing the metal fine particles cannot be obtained. Further, such a high molecular weight dispersing agent may be interposed between metal fine particles in a conductor wiring or a conductive film formed using a metal ink for inkjet, and may impede its conductivity.

  On the other hand, a dispersant having a molecular weight of 200 to 30,000 is easy to have a so-called loop-train-tail structure, and thus has an excellent effect of improving the dispersibility of the metal fine particles, and is interposed between the metal fine particles. Therefore, there is no risk of hindering conductivity. In consideration of stable dispersion of the metal fine particles, the molecular weight of the dispersant is particularly preferably 2000 to 30000 even within the above range.

  In consideration of preventing deterioration of the conductor wiring, the conductive film, or the electronic components disposed in the vicinity thereof, the dispersant does not contain S, P, B, and halogen atoms. Preferably it is a compound. Suitable dispersants that satisfy these conditions include, for example, amine-based polymer dispersants such as polyethyleneimine and polyvinylpyrrolidone, carbonization having a carboxylic acid group in the molecule such as polyacrylic acid and carboxymethylcellulose. A hydrogen-based polymer dispersant, poval (polyvinyl alcohol), or a copolymer having a polyethyleneimine moiety and a polyethylene oxide moiety in one molecule (hereinafter referred to as “PEI-PO copolymer”), A polymeric dispersant is preferred. The polymer dispersant can also function as a viscosity modifier for metal ink jet ink.

  The mixing ratio of the dispersing agent is preferably 2 to 30 parts by weight per 100 parts by weight of the metal fine particles. When the blending ratio is less than 2 parts by weight, there is a possibility that the effect of uniformly dispersing the metal fine particles in the metal ink for ink jet due to the addition of the dispersing agent may not be obtained. When exceeding, there exists a possibility that a viscosity may become high too much and the metal ink for inkjet suitable for an inkjet printing method may not be obtained. In addition, an excessive dispersant may be interposed between metal fine particles in a conductor wiring or a conductive film formed using a metal ink for inkjet, and the conductivity may be hindered.

  The molecular weight and blending ratio of the dispersant have optimum physical properties suitable for various ink-jet printing methods employed when forming a conductor wiring or a conductive film using the ink-jet metal ink of the present invention. From the above range, it is preferable to select a more suitable range suitable for each inkjet printing method. In addition, various types of dispersants are used so as to have optimum physical properties suitable for various ink-jet printing methods employed when forming conductive wirings and conductive films using the ink-jet metal ink of the present invention. It is preferable to use a suitable dispersant selected from the dispersants.

The water-soluble organic solvent is a group consisting of alcohols, ketones, glycol ethers, and water-soluble nitrogen-containing organic compounds among various water-soluble organic solvents having a dielectric constant of 3 or more at 20 ° C. At least one selected from the above is selected and used.
Among these, as alcohol , methanol, ethanol, n-propanol, 2-propanol, t-butyl alcohol, glycerol, dipropylene glycol, ethylene glycol, polyethylene glycol etc. are mentioned, for example. Examples of ketones include acetone and methyl ethyl ketone .
As glycol ethers, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, triethylene glycol monobutyl ether, dipropylene glycol Examples include monomethyl ether, dipropylene glycol monoethyl ether, and tripropylene glycol monomethyl ether .
Still nitrogen-containing organic compound, 2-pyrrolidone, water-soluble nitrogen-containing organic compounds such as N- methylpyrrolidone. The water-soluble organic solvent can be used alone or in combination of two or more.

In the present invention, water and the alcohol, ketone, glycol ether, water as a dispersion medium so as to have the optimum physical properties for the ink jet printing method for forming the conductor wiring and the conductive film using the ink jet metal ink , And at least one water-soluble organic solvent selected from the group consisting of water-soluble nitrogen-containing organic compounds , and the proportion of the water-soluble organic solvent in the mixed solvent is within the range of 75% by weight or more While being appropriately selected, the type of water-soluble organic solvent, or a combination of two or more water-soluble organic solvents is appropriately selected.

In other words, an inkjet metal ink suitable for a piezo inkjet printing method has a surface tension of 30 to 45 mN / m (25 ° C.) and a viscosity as described above in order to improve the ejection performance from the nozzle. Is preferably 0.5 to 19 mPa · s (25 ° C.), the viscosity is not easily increased, and the vapor pressure is required to be low so that the boiling point is 100 ° C. or higher. In particular, the temperature is preferably 120 to 300 ° C. As the water-soluble organic solvent satisfying these characteristics, a compound having a relatively large molecular weight such as glycol ether is preferable.

  On the other hand, an inkjet metal ink suitable for a thermal inkjet printing method similarly has a surface tension of 20 to 60 mN / m (25 ° C.) and a viscosity of 0.5 to 0.5 in order to improve ejection performance from a nozzle. In addition to being preferably 40 mPa · s (25 ° C.), in order to easily generate bubbles due to the heat generated by the heating element, a high vapor pressure is required, and the boiling point is 150 ° C. or less, in particular, 80 to 130 ° C. Preferably there is. As the water-soluble organic solvent satisfying these characteristics, a compound having a relatively small molecular weight such as a lower alcohol is preferable.

  The metal ink for inkjet according to the present invention is a process of completely separating metal fine particles from water using an aqueous metal colloid solution obtained by reducing metal ions in water and precipitating metal fine particles in water. It is preferable to manufacture without going through. More specifically, the aqueous metal colloid solution is concentrated to a predetermined concentration by, for example, using a rotary evaporator, heating, or centrifuging to remove the supernatant, and then By adding a fixed amount of a water-soluble organic solvent, the metal ink for inkjet of the present invention is produced.

  The aqueous metal colloid solution as a starting material can be produced in the same manner as in the prior art. For example, a water-soluble metal compound that is a source of metal ions and a dispersing agent are dissolved in water, and a reducing agent is added. Preferably, the metal ions are reduced for a certain time under stirring. By doing so, an aqueous metal colloidal solution is produced.

The water-soluble metal compound that is the source of metal ions is not limited to this. For example, in the case of silver, silver nitrate (I) (AgNO ₃ ) or silver methanesulfonate (CH ₃ SO ₃ Ag) In particular, silver (I) nitrate is preferable. In the case of gold, tetrachloroauric (III) acid tetrahydrate (HAuCl ₄ · 4H ₂ O) and the like can be mentioned. Further, in the case of platinum, dinitrodiammine platinum (II) (Pt (NO ₂ ) ₂ (NH ₃ ) ₂ ) or hexachloroplatinum (IV) acid hexahydrate (H ₂ [PtCl ₆ ] · 6H ₂ O) In the case of palladium, palladium (II) chloride (PdCl ₂ ) and the like can be mentioned. Moreover, you may use said water-soluble metal compound complexed with ammonia, a citric acid, etc. as needed.

  As the reducing agent, various reducing agents having water solubility can be used, but considering that the particle size is as small as possible and uniform metal fine particles are formed, a reducing agent having a weak reducing power is selected and used. It is preferable to do this.

  Examples of such a reducing agent include alcohols such as methanol, ethanol and 2-propanol, ascorbic acid, etc., ethylene glycol, glutathione, organic acids (citric acid, malic acid, tartaric acid, etc.), reducing sugars ( Glucose, galactose, mannose, fructose, sucrose, maltose, raffinose, stachyose, etc.) and sugar alcohols (sorbitol, etc.).

  In order to adjust the primary particle size of the metal fine particles to the above range, the kind and blending ratio of the metal compound, the dispersant, and the reducing agent are adjusted, and when the metal compound is reduced, the stirring speed, temperature, time Etc. may be adjusted.

  As described above, the ink-jet metal ink of the present invention can be formed by various ink-jet printing methods such as a piezo method and a thermal method, by appropriately adjusting its physical properties. It can be suitably used for forming and the like.

Below, this invention is demonstrated based on an Example and a comparative example.
(Silver ink for inkjet)

Example 1:
After 26 g of silver nitrate was dissolved in 200 g of pure water, ammonia water was added to adjust the pH of the liquid to 11.0 to prepare a silver nitrate ammonia solution. Next, after adding and dissolving 12 g of polyvinylpyrrolidone (molecular weight 30000) as a dispersant in this silver nitrate ammonia solution, 100 g of ethylene glycol as a reducing agent is added and stirred at a stirring speed of 1000 rpm. However, the reaction was carried out at 10 ° C. for 180 minutes to obtain an aqueous silver colloid solution having yellow plasmon absorption.

  Next, the obtained silver colloid solution is centrifuged under the condition of 20000 G × 20 minutes to repeat the operation of removing impurities lighter than the silver fine particles, then washed with pure water, and then the particle size of the silver fine particles When the distribution was measured using a particle size distribution measuring apparatus (trade name Microtrac UPA150EX manufactured by Nikkiso Co., Ltd.) applying the laser Doppler method, a sharp peak was observed at a position of 5 nm.

  Next, the silver colloid solution is concentrated using a rotary evaporator, the moisture content is reduced to 20% by weight, ethylene glycol monobutyl ether and glycerin as water-soluble organic solvents are added, and then completely dispersed. Stirring using a magnetic stirrer, further heating, concentrating until the concentration of silver fine particles reaches 30% by weight, and the dispersion medium is a mixed solvent of water, ethylene glycol monobutyl ether and glycerin Silver ink was manufactured.

  In the silver ink for inkjet, the mixing ratio of silver fine particles (Ag), water (W), ethylene glycol monobutyl ether (EGB), and glycerin (Gl) is a weight ratio of Ag: W: EGB: Gl = 30: 5: 60: 5. When the physical properties of the silver ink for ink jet were measured, the surface tension was 33 mN / m (25 ° C.), the viscosity was 16 mPa · s (25 ° C.), and the boiling point was 220 ° C. Moreover, when the particle size distribution of the silver fine particles in the ink-jet silver ink was measured using the particle size distribution measuring apparatus, a sharp peak was observed at a position of 5 nm. It was confirmed that the particle size distribution was not changed.

The above silver ink for ink jet was used in a piezo type ink jet printer and printed continuously for 1 hour. However, no clogging occurred at the nozzle of the printer, and no discharge failure occurred. The ejection stability was good. Further, the above silver ink for ink jet is used in a piezo type ink jet printer, printed on the surface of a glass substrate, and baked in the atmosphere at 300 ° C. for 30 minutes, so that the ratio L / S between the line L and the space S is L / S. = 50/50 μm conductor wiring was formed. The thickness of the conductor wiring was 0.3 μm when measured using a surface roughness meter (manufactured by Tokyo Seimitsu Co., Ltd.). The resistivity of the conductor wiring was 2.2 × 10 ⁻⁶ Ω · cm.

  When printed on a glass substrate and observed before firing using a scanning electron microscope, as shown in FIG. 1, it has a uniform structure composed of a large number of fine silver particles having a uniform particle size and shape. Was confirmed. And when the conductor wiring after baking was similarly observed using the scanning electron microscope, as shown in FIG. 2, many silver fine particles melt | dissolve and unite and it has become the continuous beautiful film | membrane. confirmed.

Example 2:
After 26 g of silver nitrate was dissolved in 300 g of pure water, ammonia gas was added to adjust the pH of the solution to 11.3 to prepare a silver nitrate ammonia solution. Next, 16 g of polyacrylic acid (molecular weight 5000) as a dispersant is added to the silver nitrate ammonia solution and dissolved, and then 22 g of ascorbic acid as a reducing agent is added and stirred at a stirring speed of 1000 rpm. The mixture was reacted at 5 ° C. for 5 minutes to obtain an aqueous silver colloid solution having yellow plasmon absorption.

  Next, the obtained silver colloid solution is subjected to electrodialysis using an ultrafiltration membrane to remove impurities, and then washed with pure water. As a result, a sharp peak was observed at a position of 15 nm.

  Next, this silver colloid solution was concentrated by heating to 70 ° C., the water content was reduced to 5% by weight, and 2-butoxyethanol and polyethylene glycol (average molecular weight 200) as water-soluble organic solvents were added. After that, the mixture is stirred with a magnetic stirrer until it is completely dispersed, and further heated and concentrated until the concentration of the silver fine particles becomes 30% by weight. The dispersion medium is composed of water, 2-butoxyethanol, An ink-jet silver ink, which is a mixed solvent with polyethylene glycol, was produced.

  In the silver ink for inkjet, the mixing ratio of silver fine particles (Ag), water (W), 2-butoxyethanol (BE), and polyethylene glycol (PEG) is a weight ratio of Ag: W: BE: PEG = 30: 1. : 65: 4. When the physical properties of the silver ink for ink jet were measured, the surface tension was 30 mN / m (25 ° C.), the viscosity was 15 mPa · s (25 ° C.), and the boiling point was 150 ° C. Moreover, when the particle size distribution of the silver fine particles in the ink-jet silver ink was measured using the particle size distribution measuring apparatus, a sharp peak was observed at a position of 15 nm. It was confirmed that the particle size distribution was not changed.

The above silver ink for ink jet was used in a piezo type ink jet printer and printed continuously for 1 hour. However, no clogging occurred at the nozzle of the printer, and no discharge failure occurred. The ejection stability was good. Further, the above-described silver ink for ink jet is used in a piezo ink jet printer, printed on the surface of a glass substrate, fired at 200 ° C. for 30 minutes in the atmosphere, and the ratio of line L to space S L / S = 50/50 μm conductor wiring was formed. The thickness of the conductor wiring was 0.3 μm when measured using a surface roughness meter (manufactured by Tokyo Seimitsu Co., Ltd.). The resistivity of the conductor wiring was 2.2 × 10 ⁻⁶ Ω · cm.

Example 3:
Other than using 4 g of silver nitrate, 2 g of polyethyleneimine (molecular weight 600) as a dispersant, 4 g of titanium trichloride as a reducing agent, a reaction temperature of 25 ° C., and a reaction time of 30 minutes. Obtained an aqueous silver colloid solution in the same manner as in Example 2.

  Next, the obtained silver colloid solution is subjected to electrodialysis using an ultrafiltration membrane to remove impurities, and then washed with pure water. As a result, a sharp peak was observed at a position of 8 nm.

  Next, this silver colloid solution is concentrated using a rotary evaporator, the water content is reduced to 15% by weight, ethylene glycol as a water-soluble organic solvent is added, and then a magnetic stirrer is used until completely dispersed. The mixture was stirred and further heated to concentrate until the concentration of the silver fine particles became 25% by weight to produce a silver ink for ink jet in which the dispersion medium was a mixed solvent of water and ethylene glycol.

  The mixing ratio of silver fine particles (Ag), water (W), and ethylene glycol (EG) in the ink-jet silver ink was Ag: W: EG = 25: 2: 73 in terms of weight ratio. When the physical properties of the silver ink for ink jet were measured, the surface tension was 45 mN / m (25 ° C.), the viscosity was 19 mPa · s (25 ° C.), and the boiling point was 185 ° C. Moreover, when the particle size distribution of the silver fine particles in the ink-jet silver ink was measured using the particle size distribution measuring apparatus, a sharp peak was observed at a position of 8 nm. It was confirmed that the particle size distribution was not changed.

The above silver ink for ink jet was used in a piezo type ink jet printer and printed continuously for 1 hour. However, no clogging occurred at the nozzle of the printer, and no discharge failure occurred. The ejection stability was good. Further, the ink-jet silver ink is used in a piezo-type ink jet printer, printed on the surface of a glass substrate, fired at 400 ° C. for 15 minutes in the air, and the ratio of line L to space S L / S = 100/100 μm conductor wiring was formed. The thickness of the conductor wiring was 0.2 μm when measured using a surface roughness meter (manufactured by Tokyo Seimitsu Co., Ltd.). Moreover, the resistivity of the conductor wiring was 1.8 × 10 ⁻⁶ Ω · cm.

Example 4:
As in Example 2, except that 12 g of polyethyleneimine (molecular weight 10,000) was used as the dispersant, 20 g of fructose was used as the reducing agent, the reaction temperature was 15 ° C., and the reaction time was 120 minutes. An aqueous silver colloidal solution was obtained.

  Next, the obtained silver colloid solution is centrifuged under the condition of 20000 G × 20 minutes to repeat the operation of removing impurities lighter than the silver fine particles, then washed with pure water, and then the particle size of the silver fine particles When the distribution was measured using the particle size distribution measuring apparatus, a sharp peak was observed at a position of 30 nm.

  Next, the silver colloid solution is concentrated by heating to 70 ° C., the moisture content is reduced to 3% by weight, 2-ethoxyethanol and glycerin as water-soluble organic solvents are added, and then completely dispersed. Stirring using a magnetic stirrer, further heating and concentrating until the concentration of silver fine particles is 40% by weight, and the dispersion medium is a mixed solvent of water, 2-ethoxyethanol and glycerin An ink jet silver ink was produced.

  In the silver ink for inkjet, the mixing ratio of silver fine particles (Ag), water (W), 2-ethoxyethanol (EE), and glycerin (Gl) is a weight ratio of Ag: W: EE: Gl = 40: 1: 55: 4. When the physical properties of the silver ink for ink jet were measured, the surface tension was 32 mN / m (25 ° C.), the viscosity was 14 mPa · s (25 ° C.), and the boiling point was 200 ° C. Further, when the particle size distribution of the silver fine particles in the ink-jet silver ink was measured using the particle size distribution measuring apparatus, a sharp peak was observed at a position of 30 nm. It was confirmed that the particle size distribution was not changed.

The above silver ink for ink jet was used in a piezo type ink jet printer and printed continuously for 1 hour. However, no clogging occurred at the nozzle of the printer, and no discharge failure occurred. The ejection stability was good. In addition, the above-described silver ink for ink-jet recording is printed on the surface of a resin substrate using a piezo-type ink-jet printer, and baked at 180 ° C. for 60 minutes in the atmosphere, so that the ratio L / S between the line L and the space S = 30/30 μm conductor wiring was formed. The thickness of the conductor wiring was 0.5 μm as measured using a surface roughness meter (manufactured by Tokyo Seimitsu Co., Ltd.). The resistivity of the conductor wiring was 4.0 × 10 ⁻⁶ Ω · cm.

Example 5:
After dissolving 52 g of silver nitrate in 200 g of pure water, ammonia water was added to adjust the pH of the solution to 12.0 to prepare a silver nitrate ammonia solution. Next, 25 g of polyvinylpyrrolidone (molecular weight 30000) as a dispersing agent is added to the silver nitrate ammonia solution and dissolved, and then 100 g of 2-propanol as a reducing agent is added and stirred at a stirring speed of 1000 rpm. The mixture was reacted at 40 ° C. for 60 minutes to obtain an aqueous silver colloid solution having yellow plasmon absorption.

  Next, the obtained silver colloid solution is centrifuged under the condition of 20000 G × 20 minutes to repeat the operation of removing impurities lighter than the silver fine particles, then washed with pure water, and then the particle size of the silver fine particles When the distribution was measured using the particle size distribution measuring apparatus, a sharp peak was observed at a position of 5 nm.

  Next, this silver colloid solution is concentrated using a rotary evaporator, the water content is reduced to 22% by weight, 2-ethoxyethanol and 2-pyrrolidone as water-soluble organic solvents are added, and then completely dispersed. Stir using a magnetic stirrer, and further heat and concentrate until the concentration of silver fine particles is 30% by weight. The dispersion medium is a mixed solvent of water, 2-ethoxyethanol and 2-pyrrolidone. A silver ink for ink jet was produced.

  In the silver ink for inkjet, the mixing ratio of silver fine particles (Ag), water (W), 2-ethoxyethanol (EE), and 2-pyrrolidone (Py) is a weight ratio of Ag: W: EE: Py = 30: 5: 60: 5. When the physical properties of the silver ink for ink jet were measured, the surface tension was 32 mN / m (25 ° C.), the viscosity was 8 mPa · s (25 ° C.), and the boiling point was 195 ° C. Moreover, when the particle size distribution of the silver fine particles in the ink-jet silver ink was measured using the particle size distribution measuring apparatus, a sharp peak was observed at a position of 5 nm. It was confirmed that the particle size distribution was not changed.

The above silver ink for ink jet was used in a piezo type ink jet printer and printed continuously for 1 hour. However, no clogging occurred at the nozzle of the printer, and no discharge failure occurred. The ejection stability was good. In addition, the above silver ink for ink jet is used in a piezo type ink jet printer, printed on the surface of a resin substrate, baked in the atmosphere at 200 ° C. for 30 minutes, and the ratio of line L to space S L / S = 80/80 μm conductor wiring was formed. The thickness of the conductor wiring was 0.3 μm when measured using a surface roughness meter (manufactured by Tokyo Seimitsu Co., Ltd.). The resistivity of the conductor wiring was 3.5 × 10 ⁻⁶ Ω · cm.

Example 6:
Except that the amount of silver nitrate is 26 g, polyvinylpyrrolidone (molecular weight 25000) 20 g is used as a dispersant, glutamic acid 10 g is used as a reducing agent, the reaction temperature is 25 ° C., and the reaction time is 30 minutes. In the same manner as in Example 5, an aqueous silver colloid solution was obtained.

  Next, the obtained silver colloid solution is subjected to electrodialysis using an ultrafiltration membrane to remove impurities, and then washed with pure water. As a result, a sharp peak was observed at a position of 40 nm.

  Next, after centrifuging this silver colloid solution under the condition of 10000 rpm, it is concentrated by removing the supernatant, the water content is reduced to 10% by weight, ethanol and glycerin as water-soluble organic solvents are added, It stirs using a magnetic stirrer until it completely disperses, further heats, concentrates until the concentration of silver fine particles reaches 60% by weight, and the dispersion medium is a mixed solvent of water, ethanol and glycerin. An inkjet silver ink was manufactured.

  In the silver ink for inkjet, the mixing ratio of silver fine particles (Ag), water (W), ethanol (Et), and glycerin (Gl) is a weight ratio of Ag: W: Et: Gl = 60: 5: 34: 1. Met. When the physical properties of the silver ink for ink jet were measured, the surface tension was 30 mN / m (25 ° C.), the viscosity was 3 mPa · s (25 ° C.), and the boiling point was 100 ° C. Moreover, when the particle size distribution of the silver fine particles in the ink-jet silver ink was measured using the particle size distribution measuring apparatus, a sharp peak was observed at a position of 40 nm. It was confirmed that the particle size distribution was not changed.

The above-described ink-jet silver ink was used in a thermal-type ink-jet printer and was continuously printed for 1 hour. However, no clogging occurred at the printer nozzle, and no discharge failure occurred. The ejection stability was good. In addition, the above-described silver ink for ink jet is used in a thermal ink jet printer, printed on the surface of a glass substrate, and baked at 450 ° C. for 30 minutes in the air, so that the ratio L / S between the line L and the space S is L / S. = 120/120 μm conductor wiring was formed. The thickness of the conductor wiring was 1 μm when measured using a surface roughness meter (manufactured by Tokyo Seimitsu Co., Ltd.). Moreover, the resistivity of the conductor wiring was 1.7 × 10 ⁻⁶ Ω · cm.

Example 7:
Except that the amount of silver nitrate is 26 g, 5 g of polyvinylpyrrolidone (molecular weight 30000) is used as a dispersant, 20 g of myristic acid is used as a reducing agent, the reaction temperature is 25 ° C., and the reaction time is 120 minutes. In the same manner as in Example 5, an aqueous silver colloid solution was obtained.

  Next, the obtained silver colloid solution is subjected to electrodialysis using an ultrafiltration membrane to remove impurities, and then washed with pure water. As a result, a sharp peak was observed at a position of 15 nm.

  Next, after centrifuging the silver colloid solution under the condition of 10000 rpm, the supernatant is removed to concentrate, the water content is reduced to 12% by weight, and ethanol as a water-soluble organic solvent is added. Stir using a magnetic stirrer until dispersed, and further heat to concentrate until the concentration of silver fine particles is 25% by weight, and the dispersion medium is a mixed solvent of water and ethanol. An ink was produced.

  The blending ratio of silver fine particles (Ag), water (W), and ethanol (Et) in the silver ink for inkjet was a weight ratio of Ag: W: Et = 25: 2: 73. When the physical properties of the silver ink for ink jet were measured, the surface tension was 24 mN / m (25 ° C.), the viscosity was 2 mPa · s (25 ° C.), and the boiling point was 82 ° C. Moreover, when the particle size distribution of the silver fine particles in the ink-jet silver ink was measured using the particle size distribution measuring apparatus, a sharp peak was observed at a position of 15 nm. It was confirmed that the particle size distribution was not changed.

The above-described ink-jet silver ink was used in a thermal-type ink-jet printer and was continuously printed for 1 hour. However, no clogging occurred at the printer nozzle, and no discharge failure occurred. The ejection stability was good. Further, the ink-jet silver ink is printed on the surface of a resin substrate using a thermal ink-jet printer, and baked in the atmosphere at 180 ° C. for 60 minutes, so that the ratio L / S between the line L and the space S is L / S. = 50/50 μm conductor wiring was formed. The thickness of the conductor wiring was 0.2 μm when measured using a surface roughness meter (manufactured by Tokyo Seimitsu Co., Ltd.). The resistivity of the conductor wiring was 6.5 × 10 ⁻⁶ Ω · cm.

Comparative Example 1:
The aqueous silver colloid solution having a sharp peak at a position of 15 nm obtained in Example 2 is heated to 70 ° C. to completely dry and remove the water, thereby completely separating the silver fine particles from the water. After adding butoxyethanol and polyethylene glycol (average molecular weight 200), stir using a magnetic stirrer until completely dispersed, and further heat to concentrate until the concentration of silver fine particles is 30% by weight. Thus, an ink-jet silver ink in which the dispersion medium was 2-butoxyethanol and polyethylene glycol was produced.

  The mixing ratio of silver fine particles (Ag), 2-butoxyethanol (BE), and polyethylene glycol (PEG) in the silver ink for inkjet was, as a weight ratio, Ag: BE: PEG = 30: 50: 20. When the physical properties of the silver ink for ink jet were measured, the surface tension was 65 mN / m (25 ° C.), the viscosity was 32 mPa · s (25 ° C.), and the boiling point was 150 ° C. Further, when the particle size distribution of the silver fine particles in the silver ink for inkjet was measured using the particle size distribution measuring device, a peak was observed at a position of 1500 nm, and thus when the silver fine particles were completely separated from the water. It was confirmed that agglomeration occurred and the particle size distribution varied greatly.

When the above silver ink for ink jet is used in a piezo type ink jet printer and printed continuously for 1 hour, clogging occurs at the nozzle of the printer, resulting in ejection failure and ejection stability. Was bad. Further, the above-described silver ink for ink jet is used in a piezo ink jet printer, printed on the surface of a glass substrate, fired at 200 ° C. for 30 minutes in the atmosphere, and the ratio of line L to space S L / S = 300/300 μm conductor wiring was formed. The thickness of the conductor wiring was 0.3 μm when measured using a surface roughness meter (manufactured by Tokyo Seimitsu Co., Ltd.). The resistivity of the conductor wiring was 2.5 × 10 ⁻⁵ Ω · cm.

Comparative Example 2:
The aqueous silver colloidal solution having a sharp peak at the position of 8 nm obtained in Example 3 is concentrated using a rotary evaporator to reduce the water content to 15% by weight, and then is a water-insoluble organic solvent. After adding α-terpineol, the mixture was stirred using a magnetic stirrer, but it was separated into two liquids, and a uniform inkjet silver ink could not be obtained.
(Palladium ink for inkjet)

Example 8:
After 21 g of palladium (II) chloride was dissolved in 300 g of pure water, 20 g of polyacrylic acid (molecular weight 5000) as a dispersant was added and completely dissolved. Next, after adding 80 g of 2-propanol as a reducing agent to this palladium chloride solution, the mixture is reacted at 40 ° C. for 60 minutes while stirring at a stirring speed of 1000 rpm to obtain a black, aqueous palladium colloidal solution. Got.

  Next, the obtained colloidal colloid solution is centrifuged under the condition of 20000 G × 20 minutes to repeatedly remove impurities lighter than the palladium fine particles, and then washed with pure water. When the distribution was measured using the particle size distribution measuring apparatus, a sharp peak was observed at a position of 3 nm.

  Next, the palladium colloid solution is concentrated by heating to 70 ° C., the moisture content is reduced to 10% by weight, 2-ethoxyethanol and glycerin as water-soluble organic solvents are added, and then completely dispersed. Stirring using a magnetic stirrer, further heating, and concentrating until the concentration of the palladium fine particles is 25% by weight, the dispersion medium is a mixed solvent of water, 2-ethoxyethanol and glycerin An ink-jet palladium ink was produced.

  The blending ratio of palladium fine particles (Pd), water (W), 2-ethoxyethanol (EE), and glycerin (Gl) in the palladium ink for inkjet is a weight ratio of Pd: W: EE: Gl = 25: 2: 70: 3. When the physical properties of the ink-jet palladium ink were measured, the surface tension was 32 mN / m (25 ° C.), the viscosity was 12 mPa · s (25 ° C.), and the boiling point was 200 ° C. Further, when the particle size distribution of the palladium fine particles in the ink-jet palladium ink was measured using the particle size distribution measuring apparatus, a sharp peak was observed at a position of 3 nm. It was confirmed that the particle size distribution was not changed.

The above-described ink-jet palladium ink was used in a piezo-type ink-jet printer and printed continuously for 1 hour. However, no clogging occurred at the nozzles of the printer. The ejection stability was good. The ink-jet palladium ink is used in a piezo-type ink jet printer, printed on the surface of a glass substrate, baked in the atmosphere at 250 ° C. for 30 minutes, and the ratio of line L to space S L / S = 100/100 μm conductor wiring was formed. The thickness of the conductor wiring was 0.2 μm when measured using a surface roughness meter (manufactured by Tokyo Seimitsu Co., Ltd.). The resistivity of the conductor wiring was 1.8 × 10 ⁻⁵ Ω · cm.

Example 9:
As in Example 8, except that 5 g of polyethyleneimine (molecular weight 1800) was used as the dispersant, 16 g of titanium trichloride was used as the reducing agent, the reaction temperature was 25 ° C., and the reaction time was 30 minutes. Thus, an aqueous palladium colloidal solution was obtained.

  Next, the obtained colloidal palladium solution is subjected to electrodialysis using an ultrafiltration membrane to remove impurities, and then washed with pure water. As a result, a sharp peak was observed at a position of 4 nm.

  Next, the palladium colloid solution is concentrated using a rotary evaporator to reduce the moisture content to 22% by weight, add ethanol, glycerin and acetone as water-soluble organic solvents, and then add magnesium until completely dispersed. Stirring using a tic stirrer, further heating and concentrating until the concentration of fine palladium particles reaches 60% by weight, and the dispersion medium is a palladium ink for inkjet, which is a mixed solvent of water, ethanol, glycerin and acetone. Manufactured.

  In the ink-jet palladium ink, the mixing ratio of palladium fine particles (Pd), water (W), ethanol (Et), glycerin (Gl), and acetone (Ac) is Pd: W: Et: Gl: Ac = weight ratio. 60: 10: 10: 5: 15. The physical properties of the palladium ink for inkjet were measured. The surface tension was 30 mN / m (25 ° C.), the viscosity was 1.5 mPa · s (25 ° C.), and the boiling point was 95 ° C. Further, when the particle size distribution of the palladium fine particles in the ink-jet palladium ink was measured using the particle size distribution measuring device, a sharp peak was observed at a position of 4 nm. It was confirmed that the particle size distribution was not changed.

Using the above-described ink-jet palladium ink in a thermal-type ink-jet printer, printing was continuously performed for 1 hour. However, no clogging occurred at the nozzle of the printer, and no discharge failure occurred. The ejection stability was good. The ink-jet palladium ink is printed on the surface of a glass substrate using a thermal ink-jet printer and baked in the atmosphere at 200 ° C. for 30 minutes, so that the ratio L / S between the line L and the space S is L / S. = 200/200 μm conductor wiring was formed. The thickness of the conductor wiring was 0.4 μm when measured using a surface roughness meter (manufactured by Tokyo Seimitsu Co., Ltd.). Moreover, the resistivity of the conductor wiring was 3.0 × 10 ⁻⁵ Ω · cm.

Comparative Example 3:
The aqueous palladium colloidal solution having a sharp peak at a position of 4 nm obtained in Example 9 is concentrated using a rotary evaporator to reduce the water content to 22% by weight, and then is a water-insoluble organic solvent. After adding α-terpineol, the mixture was stirred using a magnetic stirrer, but it was separated into two liquids, and a uniform ink-jet palladium ink could not be obtained.
(Gold ink for inkjet)

Example 10:
After 42 g of tetrachloroauric (III) acid tetrahydrate was dissolved in 150 g of pure water, 16 g of polyvinyl alcohol (molecular weight 22000) as a dispersant was added and completely dissolved. Next, after adding 22 g of ascorbic acid as a reducing agent to this gold chloride solution, the mixture is reacted at 5 ° C. for 15 minutes while stirring at a stirring speed of 1000 rpm, and has an absorptive plasmon absorption. A colloidal gold solution was obtained.

  Next, the obtained colloidal gold solution is subjected to electrodialysis using an ultrafiltration membrane to remove impurities, and then washed with pure water. As a result, a sharp peak was observed at a position of 5 nm.

  Next, this gold colloid solution was concentrated using a rotary evaporator, the water content was reduced to 15% by weight, and 2-butoxyethanol and polyethylene glycol (average molecular weight 200) as a water-soluble organic solvent were added. It stirs using a magnetic stirrer until it completely disperses, and further, it heats and concentrates until the density | concentration of a gold fine particle becomes 25 weight%, and a dispersion medium is water, 2-butoxyethanol, and polyethyleneglycol. Inkjet gold ink, which is a mixed solvent, was prepared.

  In the gold ink for inkjet, the mixing ratio of gold fine particles (Au), water (W), 2-butoxyethanol (BE), and polyethylene glycol (PEG) is a weight ratio of Au: W: BE: PEG = 25: 4. : 65: 6. When the physical properties of the gold ink for inkjet were measured, the surface tension was 35 mN / m (25 ° C.), the viscosity was 18 mPa · s (25 ° C.), and the boiling point was 200 ° C. Further, when the particle size distribution of the gold fine particles in the gold ink for inkjet was measured using the particle size distribution measuring apparatus, a sharp peak was observed at a position of 5 nm. It was confirmed that the particle size distribution was not changed.

The ink jet gold ink was used in a piezo type ink jet printer and printed continuously for 1 hour. However, no clogging occurred at the printer nozzles, and no discharge failure occurred. The ejection stability was good. Further, the gold ink for ink jet is used in a piezo ink jet printer, printed on the surface of a resin substrate, baked in air at 150 ° C. for 120 minutes, and the ratio of line L to space S L / S = 50/50 μm conductor wiring was formed. The thickness of the conductor wiring was 0.3 μm when measured using a surface roughness meter (manufactured by Tokyo Seimitsu Co., Ltd.). The resistivity of the conductor wiring was 7.5 × 10 ⁻⁶ Ω · cm.

Example 11:
As in Example 10, except that 10 g of polyvinylpyrrolidone (molecular weight 30000) is used as a dispersant, 80 g of 2-propanol is used as a reducing agent, the reaction temperature is 40 ° C., and the reaction time is 60 minutes. Thus, an aqueous colloidal gold solution was obtained.

  Next, the obtained colloidal gold solution is centrifuged under the condition of 20000 G × 20 minutes to repeatedly remove impurities that are lighter than gold fine particles, and then washed with pure water. When the distribution was measured using the particle size distribution measuring apparatus, a sharp peak was observed at a position of 15 nm.

  Next, the colloidal gold solution is concentrated by heating to 70 ° C., the moisture content is reduced to 3% by weight, methyl ethyl ketone as a water-soluble organic solvent is added, and then the magnetic stirrer is completely dispersed. The mixture was further heated and concentrated until the concentration of the gold fine particles became 40% by weight, and an inkjet gold ink in which the dispersion medium was a mixed solvent of water and methyl ethyl ketone was produced.

  In the gold ink for inkjet, the mixing ratio of the gold fine particles (Au), water (W), and methyl ethyl ketone (MEK) was Au: W: MEK = 40: 1: 59 in weight ratio. The physical properties of the inkjet gold ink were measured. The surface tension was 29 mN / m (25 ° C.), the viscosity was 2 mPa · s (25 ° C.), and the boiling point was 85 ° C. In addition, when the particle size distribution of the gold fine particles in the ink-jet gold ink was measured using the particle size distribution measuring apparatus, a sharp peak was observed at a position of 15 nm. It was confirmed that the particle size distribution was not changed.

The ink jet gold ink was used for a thermal type ink jet printer and printed continuously for 1 hour. However, no clogging occurred at the nozzle of the printer. The ejection stability was good. Further, the gold ink for ink jet is used in a thermal ink jet printer, printed on the surface of a glass substrate, baked in the atmosphere at 350 ° C. for 20 minutes, and the ratio L / S between the line L and the space S is L / S. = 100/100 μm conductor wiring was formed. The thickness of the conductor wiring was 0.5 μm as measured using a surface roughness meter (manufactured by Tokyo Seimitsu Co., Ltd.). Moreover, the resistivity of the conductor wiring was 3.0 × 10 ⁻⁶ Ω · cm.

Comparative Example 4:
The aqueous gold colloid solution having a sharp peak at a position of 5 nm obtained in Example 10 was treated using a rotary evaporator to completely separate the gold fine particles from the water by drying and removing all the water. After adding 2-butoxyethanol and polyethylene glycol (average molecular weight 200), the mixture is stirred with a magnetic stirrer until it is completely dispersed, and further heated, so that the concentration of gold fine particles becomes 10% by weight. The ink was concentrated to 1 to produce a gold ink for ink jetting in which the dispersion medium was 2-butoxyethanol and polyethylene glycol.

  In the gold ink for inkjet, the mixing ratio of the gold fine particles (Au), 2-butoxyethanol (BE), and polyethylene glycol (PEG) was Au: BE: PEG = 10: 85: 5 in weight ratio. Further, physical properties of the gold ink for inkjet were measured. As a result, the surface tension was 65 mN / m (25 ° C.), the viscosity was 18 mPa · s (25 ° C.), and the boiling point was 200 ° C. In addition, when the particle size distribution of the gold fine particles in the gold ink for inkjet was measured using the particle size distribution measuring apparatus, a peak was seen at a position of 600 nm, and thus the gold fine particles were completely separated from the water. It was confirmed that agglomeration occurred and the particle size distribution varied greatly.

When the above gold ink for ink jet is used in a piezo type ink jet printer and printing is performed continuously for 1 hour, the nozzle of the printer is clogged, resulting in ejection failure and ejection stability. Was bad. Further, the gold ink for ink jet is used in a piezo ink jet printer, printed on the surface of a glass substrate, baked in the atmosphere at 200 ° C. for 30 minutes, and the ratio L / S between the line L and the space S is L / S. = 400/400 μm conductor wiring was formed. The thickness of the conductor wiring was 0.1 μm when measured using a surface roughness meter (manufactured by Tokyo Seimitsu Co., Ltd.). The resistivity of the conductor wiring was 4.0 × 10 ⁻⁴ Ω · cm.

It is an electron micrograph which shows the structure of the silver fine particle in the printing before baking formed using the silver ink for inkjet of Example 1 of this invention. It is an electron micrograph which shows the structure of the film | membrane in which the silver fine particle fuse | melted and integrated in the conductor wiring formed by baking the said printing.

Claims (3)

A mixed solvent of metal particles having a primary particle size of 200 nm or less, a dispersing agent having a molecular weight of 200 to 30000, and water and a water-soluble organic solvent as a dispersion medium, obtained by reducing and precipitating metal ions in water. look including the door, and the water-soluble organic solvent, alcohols, ketones, glycol ethers, and with at least one selected from the group consisting of nitrogen-containing organic compounds in water-soluble, in the solvent mixture, a water-soluble organic A metal ink for ink jet, wherein the solvent occupies 75% by weight or more . The surface tension is 30 to 45 mN / m (25 ° C), the viscosity is 0.5 to 19 mPa · s (25 ° C) , and the boiling point is 100 ° C or higher . Metal ink for inkjet.   Claims manufactured without going through a process of completely separating metal fine particles from water using a water-based metal colloid solution obtained as a starting material by reducing metal ions in water and precipitating metal fine particles. Item 2. An inkjet metal ink according to Item 1.