CN101626856A - The manufacture method of fine silver particle, fine silver particle and the manufacturing installation of fine silver particle - Google Patents

The manufacture method of fine silver particle, fine silver particle and the manufacturing installation of fine silver particle Download PDF

Info

Publication number
CN101626856A
CN101626856A CN200880006956A CN200880006956A CN101626856A CN 101626856 A CN101626856 A CN 101626856A CN 200880006956 A CN200880006956 A CN 200880006956A CN 200880006956 A CN200880006956 A CN 200880006956A CN 101626856 A CN101626856 A CN 101626856A
Authority
CN
China
Prior art keywords
aforementioned
silver
particle
fine silver
silver particle
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN200880006956A
Other languages
Chinese (zh)
Other versions
CN101626856B (en
Inventor
樋上晃裕
宇野贵博
佐藤一祐
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Mitsubishi Materials Corp
Original Assignee
Mitsubishi Materials Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP2007095658A external-priority patent/JP2008255377A/en
Priority claimed from JP2007095660A external-priority patent/JP2008255378A/en
Application filed by Mitsubishi Materials Corp filed Critical Mitsubishi Materials Corp
Priority claimed from PCT/JP2008/056319 external-priority patent/WO2008123494A1/en
Publication of CN101626856A publication Critical patent/CN101626856A/en
Application granted granted Critical
Publication of CN101626856B publication Critical patent/CN101626856B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Landscapes

  • Manufacture Of Metal Powder And Suspensions Thereof (AREA)
  • Powder Metallurgy (AREA)
  • Non-Insulated Conductors (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

In this fine silver particle with respect to silver with 5.0 * 10 -8～1.5 * 10 -3Mol ratio contain halogen.The manufacture method of this fine silver particle has in silver ion solution adds the operation that reducing agent reduction silver ion is separated out fine silver particle, the karyomorphism of the nuclear that becomes fine silver particle become material in the presence of reduce silver ion.The manufacturing installation of this fine silver particle has: silver ion solution groove, the 1st pipeline that is connected in aforementioned silver ion solution groove, ammonia spirit groove, be connected in aforementioned ammonia spirit groove the 2nd pipeline, reduce liquid bath, be connected in the 3rd pipeline of aforementioned reduction liquid bath and the 4th pipeline that extends out from the portion of reporting to the leadship after accomplishing a task of aforementioned the 1st pipeline and aforementioned the 2nd pipeline, make from the reducing solution of aforementioned the 3rd pipeline with mixed from the mixed liquor of the silver ion solution of aforementioned the 4th pipeline and ammonia solution.

Description

The manufacture method of fine silver particle, fine silver particle and the manufacturing installation of fine silver particle
[technical field]
【0001】
The present invention relates to use the silver ion solution of high concentration to stablize and make efficiently method and this fine silver particle of small silver particles.In addition, for the technology of the reduction manufacturing silver particles of utilizing silver ion, the present invention relates to stablize and make efficiently the technology of small silver particles.In more detail, the present invention relates to stable and make method, manufacturing installation, and this fine silver particle of silver particles of the small polymolecularity of the thickener composition that is applicable to the wiring material that becomes electronic device or electrode material efficiently.
The application requires Japan's patent application 2007-095657 number, Japan's patent application 2007-095658 number, Japan's patent application 2007-095659 number of on March 30th, 2007 application, the priority of Japan's patent application 2007-095660 number, quotes its content at this.
[background technology]
【0002】
In recent years, in order to realize the high performance of e-machine, require the miniaturization and the densification of electronic device,, also require the particulate of more small and polymolecularity for the employed fine silver particle of thickener material that forms them in order to reach becoming more meticulous of distribution and electrode.
【0003】
In the past, as the manufacture method of the employed fine silver particle of e-machine material, the amine complex of known reduction silver salt made the fine silver particle precipitation, and its washing drying is obtained average grain diameter for counting the fine silver particle (patent documentation 1～3) about μ m.For example, put down in writing the silver-colored amine complex of reduction in the patent documentation 1 when fine silver particle is separated out, the method for small silver particles ℃ is made in liquid temperature to 25～60 when adjusting reduction.In addition, put down in writing in the patent documentation 3 by liquor argenti nitratis ophthalmicus and ammoniacal liquor being mixed the silver-colored amine complex solution and the reducing agent that obtain and mixed with the interior interpolation time, made BET specific area 0.25m with 20 seconds 2The method that the above small silver particles of/g is separated out.But in these manufacture methods, the size distribution of the silver particles of separating out is wide, and the easy aggegation of particle, be difficult to make particle diameter evenly and particle diameter be the problem of the following small fine silver particle of 0.2～2.5 μ m or 1 μ m.
【0004】
So, make organic reducing agent solution interflow in the known way, reduction silver in pipeline and make the method (patent documentation 4,5) of the little fine silver particle in seed crystal footpath by the stream that flows through at the silver-colored amine complex aqueous solution.But this manufacture method is owing to carry out the reduction of silver-colored amine complex in pipeline, therefore has because separating out of silver and stream narrows down and separate out in the silver strip of tube wall and peel off and sneak into the problem of thick particle etc.In addition, owing to using the low-down silver-colored amine complex aqueous solution of silver concentration in order to obtain small silver particles, it is low therefore not only to make efficient, and because a large amount of liquid that produce, so the loss increase when reclaiming, yield is also low.
[patent documentation 1] spy opens flat 8-134513 communique
[patent documentation 2] spy opens flat 8-176620 communique
[patent documentation 3] spy opens the 2001-107101 communique
[patent documentation 4] spy opens the 2005-48236 communique
[patent documentation 5] spy opens the 2005-48237 communique
[summary of the invention]
[technical problem that invention will solve]
【0005】
The invention provides manufacture method, manufacturing installation and the fine silver particle of the fine silver particle of the problems referred to above in the solution manufacture method in the past, provide the silver ion solution that uses high concentration to stablize and make efficiently method, manufacturing installation and the fine silver particle of the small silver particles of excellent dispersion.
[method of technical solution problem]
【0006】
Fine silver particle of the present invention, in fine silver particle with respect to silver with 5.0 * 10 -8～1.5 * 10 -3Mol ratio contain halogen.
In the fine silver particle of the present invention, with respect to aforementioned silver with 5.0 * 10 -8～1.8 * 10 -6Mol ratio contain aforementioned halogen, average grain diameter can be 1.5～0.5 μ m.
With respect to aforementioned silver with greater than 1.8 * 10 -6Smaller or equal to 3.0 * 10 -5Mol ratio contain aforementioned halogen, average grain diameter can be 0.5～0.15 μ m.
With respect to aforementioned silver with greater than 3.0 * 10 -5Smaller or equal to 1.5 * 10 -3Mol ratio contain aforementioned halogen, average grain diameter can be 0.15～0.08 μ m.
【0007】
The manufacture method of fine silver particle of the present invention has adds the operation that reducing agent reduction silver ion is separated out fine silver particle in silver ion solution, by the karyomorphism at the nuclear that becomes aforementioned fine silver particle become material in the presence of reduce silver ion, aforementioned fine silver particle is separated out.
【0008】
The 1st mode of the manufacture method of fine silver particle of the present invention is by the aforementioned silver ion of reduction in the presence of halide ion, makes silver halide become material to generate as aforementioned karyomorphism, and aforementioned fine silver particle is separated out.
In the 1st the mode of the manufacture method of fine silver particle, can be by adjusting halide concentration, the particle diameter of the aforementioned fine silver particle that control is separated out with respect to silver concentration.
Can use the liquor argenti nitratis ophthalmicus that adds ammoniacal liquor as aforementioned silver ion solution, can use hydroquinone solution, can use ammonium chloride (NH as compound with aforementioned halide ion as aforementioned reducing agent 4Cl), ammonium bromide (NH 4Br), ammonium iodide (NH 4I), potassium chloride (KCl), KBr (KBr), KI (KI), sodium chloride (NaCl), sodium bromide (NaBr) or sodium iodide (NaI).
Can use iodide ion as aforementioned halide ion, when reducing aforementioned silver ion, can (i) iodine be adjusted into 5.0 * 10 with respect to the mol ratio (iodine silver mol ratio, I/Ag) of silver -8～1.8 * 10 -6The fine silver particle of average grain diameter 1.5～0.5 μ m is separated out, perhaps (ii) aforementioned iodine silver mol ratio is adjusted into greater than 1.8 * 10 -6Smaller or equal to 3.0 * 10 -5The fine silver particle of average grain diameter 0.5～0.15 μ m is separated out, perhaps (iii) aforementioned iodine silver mol ratio is adjusted into greater than 3.0 * 10 -5Smaller or equal to 1.5 * 10 -3The fine silver particle of average grain diameter 0.15～0.08 μ m is separated out.
Can use the liquor argenti nitratis ophthalmicus more than the silver concentration 50g/L that adds ammoniacal liquor as aforementioned silver ion solution, can use hydroquinone solution as aforementioned reducing agent, can use iodide ion as aforementioned halide ion, by iodine is adjusted into 5.0 * 10 with respect to the mol ratio (I/Ag) of silver -8～1.5 * 10 -3, the yield that can make the fine silver particle of average grain diameter 1.5～0.08 μ m is more than 99%.
【0009】
The 2nd mode of the manufacture method of fine silver particle of the present invention is to unite to use main reducing agent and the secondary reducing agent stronger than main reducing agent reducing power, in aforementioned silver ion solution, in the presence of a spot of aforementioned auxiliary reducing agent, add aforementioned main reducing agent, the aforementioned silver ion of reduction in the presence of this main reducing agent and secondary reducing agent, make the fine silver particle of colloid shape become material to generate thus, aforementioned fine silver particle is separated out as aforementioned karyomorphism.
In the 2nd the mode of the manufacture method of fine silver particle of the present invention, can be by adjusting the addition of aforementioned auxiliary reducing agent, the particle diameter of the aforementioned fine silver particle that control is separated out.
Secondary reducing agent can be controlled in 2.5 * 10 with respect to the mol ratio (ratio of secondary reducing agent silver) of silver concentration -7～5.0 * 10 -1, the fine silver particle of average grain diameter 1.5～0.05 μ m is separated out.
Can (i) ratio of aforementioned auxiliary reducing agent silver be adjusted into 2.5 * 10 -7～3.0 * 10 -5The fine silver particle of average grain diameter 1.5～0.5 μ m is separated out, perhaps (ii) the ratio of aforementioned auxiliary reducing agent silver is adjusted into greater than 3.0 * 10 -5Smaller or equal to 4.2 * 10 -2The fine silver particle of average grain diameter 0.5～0.1 μ m is separated out, perhaps (iii) the ratio of aforementioned auxiliary reducing agent silver is adjusted into greater than 4.2 * 10 -2Smaller or equal to 5.0 * 10 -1The fine silver particle of average grain diameter 0.1～0.05 μ m is separated out.
Can use the liquor argenti nitratis ophthalmicus that adds ammoniacal liquor as aforementioned silver ion solution, can use hydroquinone solution, can use hydrazine as the aforementioned auxiliary reducing agent as aforementioned main reducing agent.
Can use the solution that mixed with little amount has the hydrazine solution of aforementioned auxiliary reducing agent in the hydroquinone solution of aforementioned main reducing agent, perhaps in aforementioned silver ion solution, add the hydroquinone solution of adding aforementioned main reducing agent immediately behind the hydrazine solution of aforementioned auxiliary reducing agent on a small quantity.
【0010】
The 3rd mode of the manufacture method of fine silver particle of the present invention is to add Nano silver grain to become material as aforementioned karyomorphism in aforementioned silver ion solution, and the aforementioned silver ion of reduction makes aforementioned fine silver particle separate out thus in the presence of this Nano silver grain.
In the 3rd the mode of the manufacture method of fine silver particle,, can control the particle diameter of the aforementioned fine silver particle of separating out by adjusting the addition of aforementioned Nano silver grain with respect to silver concentration.
Can use the liquor argenti nitratis ophthalmicus that adds ammoniacal liquor as aforementioned silver ion solution, can use hydroquinone solution, can add the following Nano silver grain of average grain diameter 50nm as aforementioned reducing agent.
The ratio of the number of can (i) that the number of aforementioned Nano silver grain is contained with respect to aforementioned silver ion solution silver ion (Nano silver grain silver ion than) is adjusted into 5.0 * 10 -7～3.0 * 10 -6The fine silver particle of average grain diameter 1.5～0.5 μ m is separated out, perhaps (ii) aforementioned Nano silver grain silver ion ratio is adjusted into greater than 3.0 * 10 -6Smaller or equal to 2.5 * 10 -5The fine silver particle of average grain diameter 0.5～0.1 μ m is separated out, perhaps (iii) aforementioned Nano silver grain silver ion ratio is adjusted into greater than 2.5 * 10 -5Smaller or equal to 1.5 * 10 -4The fine silver particle of average grain diameter 0.1～0.02 μ m is separated out.
As aforementioned Nano silver grain, can use the Nano silver grain below the average grain diameter 20nm that in the presence of natrium citricum, in liquor argenti nitratis ophthalmicus, adds ferrous sulfate reduction silver ion and generate.
【0011】
The 4th mode of the manufacture method of fine silver particle of the present invention is to add ammonia in aforementioned silver ion solution, add behind the aforementioned ammonia 20 seconds with the aforementioned reducing agent of interior interpolation, make silver hydroxide or silver oxide become material to generate thus, aforementioned fine silver particle is separated out as aforementioned karyomorphism.
In the 4th the mode of the manufacture method of fine silver particle, can be by adjusting from the time of the interpolation that is added into aforementioned reducing agent of aforementioned ammonia the particle diameter of the fine silver particle that control is separated out.
For time (elapsed time) from the interpolation that is added into aforementioned reducing agent of aforementioned ammonia, can (i) making the aforementioned elapsed time is to separate out with the interior fine silver particle of average grain diameter 0.2～0.5 μ m that makes in 0.3～0.5 second, the aforementioned elapsed time was longer than 0.5 second and is to separate out with the interior fine silver particle of average grain diameter 0.5 μ m～1.5 μ m that makes in 2 seconds, the aforementioned elapsed time was longer than 2 seconds and is to separate out with the interior fine silver particle of average grain diameter 1.5 μ m～2.0 μ m that makes in 5 seconds, the aforementioned elapsed time was longer than 5 seconds and is to separate out with the interior fine silver particle of average grain diameter 2.0 μ m～2.5 μ m that makes in 20 seconds.
【0012】
The manufacturing installation of fine silver particle of the present invention is for adding the manufacturing installation that ammonia and reducing agent reduction silver ion are separated out fine silver particle in silver ion solution, have: the silver ion solution groove, be connected in the 1st pipeline of aforementioned silver ion solution groove, the ammonia spirit groove, be connected in the 2nd pipeline of aforementioned ammonia spirit groove, the reduction liquid bath, be connected in the 3rd pipeline of aforementioned reduction liquid bath, with the 4th pipeline that the portion of reporting to the leadship after accomplishing a task from aforementioned the 1st pipeline and aforementioned the 2nd pipeline extends out, make from the reducing solution of aforementioned the 3rd pipeline with mixed from the mixed liquor of the silver ion solution of aforementioned the 4th pipeline and ammonia solution.
In the manufacturing installation of fine silver particle of the present invention, it is relative that the peristome that aforementioned the 3rd pipeline and aforementioned the 4th pipeline can be set to the end of its pipeline leaves ground mutually a little, by the portion of reporting to the leadship after accomplishing a task of aforementioned the 1st pipeline and aforementioned the 2nd pipeline extremely the flow path length of the end of aforementioned the 4th pipeline be adjustable.
[invention effect]
【0013】
Fine silver particle of the present invention is for by the fine silver particle made of reduction silver ion in the presence of halide ion, with respect to silver with 5.0 * 10 -8～1.5 * 10 -3Mol ratio contain halogen, be the fine silver particle of small favorable dispersibility.
【0014】
The manufacture method of the fine silver particle of the of the present invention the 1st mode for making the method for the fine silver particle of small favorable dispersibility by reduction silver ion in the presence of halide ion, can be stablized and makes this fine silver particle efficiently.The manufacture method of the fine silver particle of the mode according to the of the present invention the 1st when the reduction of silver ion, preferentially generates silver halide, and it becomes karyomorphism and becomes material and form nuclear.Be the crystallinity primary particle of karyomorphism Cheng Yin with the silver halide then, aggegation forms fine silver particle between this primary particle.Comparing with the situation that does not have halide ion, can form incipient nucleus easily and effectively with little energy, in addition, can increase the quantity of this incipient nucleus, counts in the aggegation center that also can increase primary particle.Therefore, stable and separate out small fine silver particle efficiently.
【0015】
In addition, the manufacture method of the fine silver particle of the mode according to the of the present invention the 1st is by adjusting the halide ion concentration with respect to silver concentration, the particle diameter of the fine silver particle that control is separated out.Therefore, by adjusting above-mentioned halogen concentration, for example, can stably obtain to be fit to the fine silver particle of particle diameter of the purposes such as fine silver particle of the fine silver particle of fine silver particle, average grain diameter 0.5～0.15 μ m of average grain diameter 1.5～0.5 μ m or average grain diameter 0.15～0.08 μ m efficiently.
【0016】
And then the manufacture method of the fine silver particle of the mode according to the of the present invention the 1st uses the silver ion solution of high concentration can make small fine silver particle efficiently.Particularly, for example, use the above liquor argenti nitratis ophthalmicus of silver concentration 50g/L that adds ammoniacal liquor, can obtain the fine silver particle of average grain diameter 1.5～0.08 μ m with the yield more than 99%.
【0017】
In addition, the manufacture method of the fine silver particle of the of the present invention the 1st mode, in the presence of halide ion, reduce silver ion, therefore can add source of halide ions (compound) with reducing solution with halide ion, need not in pipeline, to inject the so special device of reducing solution and constitute, therefore can easily implement.
【0018】
The manufacture method of the fine silver particle of the of the present invention the 2nd mode is to unite to use main reducing agent and this secondary reducing agent stronger than main reducing agent reducing power, adds in the presence of a spot of secondary reducing agent in silver ion solution and becomes owner of reducing agent, and fine silver particle is separated out.Since the strong secondary reducing agent of reducing power, initial a large amount of small fine silver particles that generate the colloid shape, and it becomes karyomorphism and becomes material and form nuclear.Small fine silver particle with the colloid shape is the crystallinity primary particle of karyomorphism Cheng Yin then, and aggegation forms fine silver particle between this primary particle.Comparing when not existing than the strong secondary reducing agent of main reducing agent reducing power, can form incipient nucleus easily and effectively with little energy, in addition, can increase the quantity of this incipient nucleus, counts in the aggegation center that also can increase primary particle.Therefore, can stablize and obtain small fine silver particle efficiently.
【0019】
In addition, the manufacture method of the fine silver particle of mode according to the of the present invention the 2nd, by adjusting the addition of secondary reducing agent, can control the particle diameter of the fine silver particle of separating out, for example, can stablize the fine silver particle of particle diameter of the purposes such as fine silver particle of the fine silver particle of making the fine silver particle be suitable for average grain diameter 1.5～0.5 μ m, average grain diameter 0.5～0.1 μ m or average grain diameter 0.1～0.05 μ m efficiently.
【0020】
And then the manufacture method of the fine silver particle of the mode according to the of the present invention the 2nd uses the silver ion solution of high concentration can make small fine silver particle efficiently.Particularly, for example, use the above liquor argenti nitratis ophthalmicus of silver concentration 50g/L that adds ammoniacal liquor, can obtain the fine silver particle of average grain diameter 1.5～0.05 μ m with the yield more than 99%.
【0021】
In addition, the manufacture method of the fine silver particle of the of the present invention the 2nd mode can be united and be used main reducing agent and secondary reducing agent, adds in the presence of secondary reducing agent and becomes owner of reducing agent, need not in pipeline, to inject this special device of reducing solution and constitute, therefore can easily implement.
【0022】
The manufacture method of the fine silver particle of the of the present invention the 3rd mode for having the operation that the reduction silver ion is made fine silver particle, is added Nano silver grain, and reduction silver ion method in the presence of this Nano silver grain can be stablized and makes small fine silver particle efficiently.In the manufacture method of the fine silver particle of the mode the of the present invention the 3rd, have a large amount of small Nano silver grains during the reduction of silver ion in solution, it becomes karyomorphism and becomes material and form nuclear.With the Nano silver grain is the crystallinity primary particle of karyomorphism Cheng Yin, and aggegation forms fine silver particle between this primary particle.Comparing with the situation that does not have Nano silver grain, formed incipient nucleus, in addition, can increase the quantity of this incipient nucleus arbitrarily, counts in the aggegation center that also can increase primary particle.Therefore, stable and separate out small fine silver particle efficiently.
【0023】
In addition, the manufacture method of the fine silver particle of mode according to the of the present invention the 3rd, by adjusting the amount of the Nano silver grain that adds, can control the particle diameter of the fine silver particle of separating out, for example, can be efficiently and stably obtain to be suitable for the fine silver particle of particle diameter of the purposes such as fine silver particle of the fine silver particle of fine silver particle, average grain diameter 0.5～0.1 μ m of average grain diameter 1.5～0.5 μ m or average grain diameter 0.1～0.02 μ m.
【0024】
And then the manufacture method of the fine silver particle of the mode according to the of the present invention the 3rd uses the silver ion solution of high concentration can make small fine silver particle efficiently.Particularly, for example, use the above liquor argenti nitratis ophthalmicus of silver concentration 50g/L that adds ammoniacal liquor, can be with the fine silver particle below the acquisition of the yield more than the 99% average grain diameter 1.5 μ m.
【0025】
In addition, the manufacture method of the fine silver particle of the of the present invention the 3rd mode can be added Nano silver grain, and the adding method of silver ion solution and reducing solution need not to inject this special device of reducing solution and constitutes without limits in pipeline, can easily implement.
【0026】
In the manufacture method of the fine silver particle of the of the present invention the 4th mode, after adding ammonia 20 seconds with interior interpolation reducing agent, form the silver hydroxide (AgOH) or the silver oxide (Ag that generate for the moment before the silver-colored amine complex thus 2O) becoming karyomorphism becomes material and forms nuclear.Be that nuclear, the size that forms seed crystal are the crystallinity primary particle of the silver of 25nm～150nm with silver hydroxide or silver oxide then, aggegation forms fine silver particle between this primary particle.Generation number as fruit stone is many, and correspondingly count and increase in the aggegation center, and then the size of fine silver particle diminishes.Therefore, if after interpolation becomes the silver hydroxide of nuclear and a large amount of ammonia that exist of silver oxide 20 seconds with interior interpolation reducing agent, then can stablize and obtain small fine silver particle efficiently.Particularly, for example, can be with the small silver particles below the acquisition of the yield more than the 99% average grain diameter 2.5 μ m.On the other hand, if long to the time of adding reducing agent behind the interpolation ammonia, then the silver hydroxide or the silver oxide of the generation of mixing initial stage almost all change silver-colored amine complex into, therefore can't work uncontrollable karyogenesis number as nuclear.Therefore, can't stablize the particle footpath of synthetic fine silver particle.
【0027】
In addition, the manufacture method of the fine silver particle of the mode according to the of the present invention the 4th is adjusted by adding behind the ammonia to the elapsed time of adding reducing agent, can make the fine silver particle of average grain diameter 0.2 μ m～2.5 μ m.
【0028】
In addition, in the manufacturing installation of the present invention, from the reducing solution of the 3rd pipeline with mix from the silver ion solution of the 4th pipeline and the mixed liquor of ammonia solution, therefore can easily implement the manufacture method of the fine silver particle of the above-mentioned the 4th mode.In addition, in the manufacturing installation of the present invention, because the flow path length of the end of the variable portion to the of reporting to the leadship after accomplishing a task 4 pipelines by the 1st pipeline and the 2nd pipeline, can easily adjust behind the interpolation ammonia to the elapsed time of adding reducing agent.
[description of drawings]
【0029】
[Fig. 1] Fig. 1 is the figure of the relation of expression iodide ion addition and Ag particle diameter.
[Fig. 2] Fig. 2 is the figure of the relation of expression kind of halogen and Ag particle diameter.
[Fig. 3] Fig. 3 is the electron micrograph (length of lower end white hollow out is 1 μ m) of the particle state of expression duplicate 1.
[Fig. 4] Fig. 4 is the electron micrograph (length of lower end white hollow out is 1 μ m) of the particle state of expression Sample A 2.
[Fig. 5] Fig. 5 is the electron micrograph (length of lower end white hollow out is 1 μ m) of the particle state of expression Sample A 5.
[Fig. 6] Fig. 6 is the electron micrograph (length of lower end white hollow out is 1 μ m) of the particle state of expression Sample A 7.
[Fig. 7] Fig. 7 is the electron micrograph (length of lower end white hollow out is 1 μ m) of the particle state of expression duplicate 2.
[Fig. 8] Fig. 8 is the electron micrograph (length of lower end white hollow out is 1 μ m) of the particle state of expression sample B 1.
[Fig. 9] Fig. 9 is the electron micrograph (length of lower end white hollow out is 1 μ m) of the particle state of expression sample B 2.
[Figure 10] Figure 10 is the electron micrograph (length of lower end white hollow out is 1 μ m) of the particle state of expression sample B 3.
[Figure 11] Figure 11 is expression N 2H 4The figure of the relation of addition and Ag particle diameter.
[Figure 12] Figure 12 is the figure of the relation of vice reducing agent addition and Ag particle diameter.
[Figure 13] Figure 13 is the electron micrograph (length of the white hollow out of lower end is 1 μ m) of the particle state of expression duplicate 6.
[Figure 14] Figure 14 is the electron micrograph (length of the white hollow out of lower end is 1 μ m) of the particle state of expression sample D2.
[Figure 15] Figure 15 is the electron micrograph (length of the white hollow out of lower end is 1 μ m) of the particle state of expression sample D5.
[Figure 16] Figure 16 is the electron micrograph (length of the white hollow out of lower end is 1 μ m) of the particle state of expression sample D8.
[Figure 17] Figure 17 is the electron micrograph (length of the white hollow out of lower end is 1 μ m) of the particle state of expression sample D9.
[Figure 18] Figure 18 is the figure of the relation of expression Ag nanoparticle subnumber and Ag particle diameter.
[Figure 19] Figure 19 is the figure of the relation of expression Ag nanoparticle subnumber and Ag particle diameter.
[Figure 20] Figure 20 is the particle state electron micrograph (length of the white hollow out of lower end is 1 μ m) of expression duplicate 13.
[Figure 21] Figure 21 is the electron micrograph (length of the white hollow out of lower end is 1 μ m) of the particle state of expression sample G1.
[Figure 22] Figure 22 is the electron micrograph (length of the white hollow out of lower end is 1 μ m) of the particle state of expression sample G2.
[Figure 23] Figure 23 is the electron micrograph (length of the white hollow out of lower end is 1 μ m) of the particle state of expression sample G3.
[Figure 24] Figure 24 is the schematic diagram that device of the present invention constitutes.
[Figure 25] Figure 25 is the figure that adds the average grain diameter of elapsed time behind the ammonia and fine silver particle among the embodiment.
[Figure 26] Figure 26 is the electron micrograph of particle state of the silver particles of expression sample L1.
[Figure 27] Figure 27 is the electron micrograph of particle state of the silver particles of expression sample L2.
[Figure 28] Figure 28 is the electron micrograph of particle state of the silver particles of expression sample L3.
[Figure 29] Figure 29 is the electron micrograph of particle state of the silver particles of expression sample L4.
[Figure 30] Figure 30 is the electron micrograph of particle state of the silver particles of expression sample L7.
[symbol description]
【0030】
The hybrid position of hybrid position, B silver ion solution and the reducing solution of 10 silver ion solution grooves, 11 ammonia spirit grooves, 12 reduction liquid baths, 13 the 1st pipelines, 14 the 2nd pipelines, 15 the 3rd pipelines, 16 the 4th pipelines, A silver ion solution and ammonia spirit.
[specific embodiment]
【0031】
Below specifically describe the present invention with embodiment.
(the 1st embodiment)
Fine silver particle of the present invention is the fine silver particle made of reduction silver ion in the presence of halide ion, with respect to silver with 5.0 * 10 -8～1.5 * 10 -3Mol ratio contain halide, be the fine silver particle of small favorable dispersibility.
【0032】
Add reducing agent reduction silver ion and make in the method that fine silver particle separates out in silver ion solution, the reduction silver ion can be made fine silver particle of the present invention in the presence of halide ion.In addition, in this manufacture method,, can control the particle diameter of the fine silver particle of separating out by adjusting halide ion concentration with respect to silver concentration.
【0033】
As silver ion solution, can use the liquor argenti nitratis ophthalmicus of adding ammoniacal liquor etc.Because the existence of ammonia forms silver-colored amine complex, be reduced and separate out by adding reducing agent silver.
【0034】
Can use hydroquinone solution, pyrogallol solution, 3 as reducing solution, the solution of the organic reducing agent with phenolic hydroxyl group of 4-dihydroxy benzenes phenol solution and so on etc.Silver ion in the addition preferred solution of reducing agent is fully reduced and is separated out the amount of fine silver particle.
【0035】
As source of halide ions (compound), can use ammonium chloride (NH with halide ion 4Cl), ammonium bromide (NH 4Br), ammonium iodide (NH 4I), potassium chloride (KCl), KBr (KBr), KI (KI), sodium chloride (NaCl), sodium bromide (NaBr) or sodium iodide (NaI) etc.It should be noted that the effect according to the order microminiaturization of iodine, bromine, chlorine has the tendency of enhancing.
【0036】
Owing to there is halide ion, when the reduction of silver ion, preferentially generate silver halide, it becomes karyomorphism and becomes material and form nuclear.Be the crystallinity primary particle of karyomorphism Cheng Yin with the silver halide then, aggegation forms fine silver particle between this primary particle.Comparing with the situation that does not have halide ion, can form incipient nucleus easily and effectively with little energy, in addition, can increase the quantity of this incipient nucleus, counts in the aggegation center that also can increase primary particle.Therefore, stable and separate out small fine silver particle efficiently.
【0037】
If there is no halide ion, when then forming silver that the reduction of silver ion produces bunch nuclear, the essential big energy of karyogenesis can't easily form incipient nucleus.For this reason, the quantity of incipient nucleus tails off, and counts and also tail off in the aggegation center of primary particle, therefore is difficult to obtain small fine silver particle.
【0038】
As the concentration of halide ion, for example, in liquor argenti nitratis ophthalmicus, add in the solution of ammoniacal liquor, when adding hydroquinone solution reduction silver ion, iodine with respect to the mol ratio (iodine silver mol ratio, I/Ag) of silver 5.0 * 10 -8More than be suitable, can obtain the following fine silver particle of average grain diameter 1.6 μ m.In addition, iodine can obtain small fine silver particle more with respect to the mol ratio of silver is high more.Particularly, iodine is 1.0 * 10 with respect to the mol ratio of silver -7During above scope, for example, use the above liquor argenti nitratis ophthalmicus of silver concentration 50g/L, can be with the fine silver particle of the acquisition of the yield 99% or more average grain diameter 1.5 μ m～0.08 μ m.
【0039】
On the other hand, if halid addition is too much, then the shape of fine silver particle is difficult to become sphere, perhaps is easy to aggegation.Therefore, halide ion is 1.5 * 10 with respect to the mol ratio of silver -3Below be suitable.
【0040】
In the manufacture method of the fine silver particle of the 1st embodiment,, can control the particle diameter of the fine silver particle of separating out by adjusting halogen concentration with respect to silver concentration.For example, when interpolation hydroquinone solution reduction silver ion is separated out fine silver particle in the liquor argenti nitratis ophthalmicus that adds ammoniacal liquor, adjust iodine can obtain average grain diameter 0.08 μ m～1.5 μ m with respect to the mol ratio (I/Ag) of silver fine silver particle as follows.
【0041】
(i) by iodine silver mol ratio (I/Ag) is adjusted into 5.0 * 10 -8～1.8 * 10 -6, the fine silver particle of average grain diameter 1.5～0.5 μ m is separated out.
(ii) by iodine silver mol ratio is adjusted into greater than 1.8 * 10 -6Smaller or equal to 3.0 * 10 -5, the fine silver particle of average grain diameter 0.5～0.15 μ m is separated out.
(iii) by above-mentioned iodine silver mol ratio is adjusted into greater than 3.0 * 10 -5Smaller or equal to 1.5 * 10 -3, the fine silver particle of average grain diameter 0.15～0.08 μ m is separated out.
【0042】
The manufacture method of the fine silver particle of the 1st embodiment of the present invention, the controlled excellence of the particle diameter of the fine silver particle of separating out, the particle diameter of the fine silver particle of separating out is in-10%～10% scope of the average grain diameter of obtaining for 10 times with identical silver-colored halide mole ratio runs.In addition, the ageing stability excellence of the soup of the manufacture method of the fine silver particle by the 1st embodiment modulation, modulate back 9 hours with the change of size of interior synthetic fine silver particle in-10%～10%.
【0043】
The manufacture method of the fine silver particle of the 1st embodiment, owing to there is halide ion during the reduction of silver ion, though therefore the fine silver particle of separating out contains halide, silver ion is reduced silver, particulate is separated out and little by little growth, so halogen is contained in the inside of fine silver particle.Therefore, halogen is difficult to stripping, does not almost have the influence of halogen when using fine silver particle.
【0044】
(the 2nd embodiment)
The manufacture method of the fine silver particle of the 2nd embodiment has adds the operation that reducing agent reduction silver ion is separated out fine silver particle in silver ion solution, unite and use main reducing agent and the secondary reducing agent stronger than main reducing agent reducing power, in silver ion solution, in the presence of a spot of secondary reducing agent, add and become owner of reducing agent, small fine silver particle is separated out.By adjusting the addition of secondary reducing agent, the particle diameter of the fine silver particle that control is separated out.
【0045】
As silver ion solution, can use the liquor argenti nitratis ophthalmicus of adding ammoniacal liquor etc.In this solution, form silver-colored amine complex, be reduced by interpolation reducing agent silver and separate out.
【0046】
In the manufacture method of the fine silver particle of the 2nd embodiment, unite and use main reducing agent and be somebody's turn to do the secondary reducing agent stronger than main reducing agent reducing power.As main reducing agent, can use hydroquinone solution (OH (C 6H 4) OH), pyrogallol solution, 3, the solution of the organic reducing agent with phenolic hydroxyl group of 4-dihydroxy benzenes phenol solution and so on.As secondary reducing agent, can use solution (N 2H 4), sodium borohydride (NaBH 4), boron hydride dimethyl amine (BH 3HN (CH 3) 2) etc., the hydrazine that preferred reducing power is strong etc.
【0047】
Use main reducing agent and this secondary reducing agent stronger by uniting than main reducing agent reducing power, in silver ion solution, in the presence of secondary reducing agent, add main reducing agent, initial silver is reduced the strong secondary reducing agent reduction of ability, can form incipient nucleus easily and effectively with little energy, in addition, can increase the quantity of this incipient nucleus, count in the aggegation center that also can increase primary particle.Therefore, for example, can stablize and obtain the following small fine silver particle of average grain diameter 0.5 μ m efficiently.
【0048】
It should be noted that if there is no secondary reducing agent, then the reduction of the silver ion that causes by the main reducing agent a little less than the reducing power generates silver bunch nuclear.At this moment, the essential lot of energy of karyogenesis can't easily form incipient nucleus.For this reason, the quantity of incipient nucleus reduces, and count and also reduce in the aggegation center of primary particle, so be difficult to obtain small fine silver particle.
【0049】
The amount of main reducing agent is that the amount of the fully silver ion of reduction silver ion solution gets final product.The amount of secondary reducing agent is that the initial amount that generates the colloid shape fine silver particle of q.s gets final product.If the amount of secondary reducing agent is too much, then fine silver particle becomes agglutination body, is difficult to obtain the small fine silver particle of favorable dispersibility.Particularly, by with the mol ratio (ratio of secondary reducing agent silver: [secondary reducing agent]/[Ag]) be controlled to be 2.5 * 10 of secondary reducing agent with respect to silver concentration -7～5.0 * 10 -1Can make the fine silver particle of average grain diameter 1.5～0.05 μ m.
【0050】
For example, use to add ammoniacal liquor liquor argenti nitratis ophthalmicus, as main reducing agent use hydroquinone solution, when using hydrazine as secondary reducing agent, hydrazine is with respect to mol ratio (the hydrazine silver ratio: N of silver concentration 2H 4/ Ag) be 2.5 * 10 -7～5.0 * 10 -1Amount be suitable, in the scope of this addition, can obtain the fine silver particle of average grain diameter 1.5～0.05 μ m with the yield more than 99%.
【0051】
In addition, if after adding main reducing agent the compartment time add secondary reducing agent, then can't obtain above-mentioned effect.Therefore, preferably in main reducing agent, add a spot of secondary reducing agent use or add a spot of secondary reducing agent after add main reducing agent immediately.
【0052】
In the manufacture method of the fine silver particle of the 2nd embodiment,, can control the particle diameter of the fine silver particle of separating out by adjusting the ratio of secondary reducing agent silver.For example, when adding the hydroquinone solution reduction silver ion that contains hydrazine in adding the liquor argenti nitratis ophthalmicus of ammoniacal liquor fine silver particle being separated out, following adjustment hydrazine silver is than (N 2H 4/ Ag) can obtain the fine silver particle of average grain diameter 1.5～0.05 μ m.
【0053】
(i) by hydrazine is silver-colored in being adjusted into 2.5 * 10 -7～3.0 * 10 -5, can obtain the fine silver particle of average grain diameter 1.5～0.5 μ m.
(ii) by hydrazine is silver-colored in being adjusted into greater than 3.0 * 10 -5Smaller or equal to 4.2 * 10 -2, can obtain the fine silver particle of average grain diameter 0.5～0.1 μ m.
(iii) by hydrazine is silver-colored in being adjusted into greater than 4.2 * 10 -2Smaller or equal to 5.0 * 10 -1, can obtain the fine silver particle of average grain diameter 0.1～0.05 μ m.
【0054】
(the 3rd embodiment)
The manufacture method of the fine silver particle of the 3rd embodiment has adds the operation that reducing agent reduction silver ion is separated out fine silver particle in silver ion solution, in the presence of this Nano silver grain, reduce silver ion by adding Nano silver grain, small fine silver particle is separated out.By adjusting addition, can control the particle diameter of the fine silver particle of separating out with respect to the Nano silver grain of silver concentration.
【0055】
As silver ion solution, can use the liquor argenti nitratis ophthalmicus of adding ammoniacal liquor etc.In this solution, form silver-colored amine complex, be reduced by interpolation reducing agent silver and separate out.As reducing solution, can use hydroquinone solution, pyrogallol solution, 3, the solution of the organic reducing agent with phenolic hydroxyl group of 4-dihydroxy benzenes phenol solution and so on.
【0056】
Nano silver grain is the silver particles (silver colloid particle) of nanometer size, can make an addition to silver ion solution.Below the preferred average grain diameter 50nm of Nano silver grain that uses, average grain diameter 2.5nm～20nm is suitable.
【0057】
Nano silver grain can use in the presence of natrium citricum, adds ferrous sulfate reduction silver ion and Nano silver grain below the average grain diameter 20nm that generates in liquor argenti nitratis ophthalmicus.Can be pre-mixed ferrous sulfate and natrium citricum, in this mixed solution, drop into liquor argenti nitratis ophthalmicus under the room temperature, the reduction silver nitrate.The silver concentration of liquor argenti nitratis ophthalmicus is that 1～200g/L is suitable, and the amount of ferrous sulfate gets final product for can fully reducing the amount of silver nitrate.In addition, the amount of natrium citricum is suitable for 2 times～7 times of molal quantity of silver.Preferred each supply nozzle that mixes of liquor argenti nitratis ophthalmicus and copperas solution drops into 5～20mL/min..After the mixing, stir, it is reacted equably.Be reduced by this reaction silver, particle diameter can obtain to contain the silver colloidal solution of the silver-colored ultramicron (Nano silver grain) of nanometer size.With this silver colloidal solution Separation of Solid and Liquid, the solid constituent that separates is washed with natrium citricum, can obtain to be dispersed with the silver colloidal solution of Nano silver grain.
【0058】
By in silver ion solution, adding Nano silver grain, be the crystallinity primary particle of karyomorphism Cheng Yin with this Nano silver grain, aggegation forms fine silver particle between this primary particle.Comparing with the situation that does not have Nano silver grain, formed incipient nucleus, in addition, can increase the quantity of this incipient nucleus arbitrarily, counts in the aggegation center that also can increase primary particle.Therefore, become small fine silver particle, for example, can stablize and obtain the following small fine silver particle of average grain diameter 1.5 μ m efficiently.It should be noted that if there is no Nano silver grain, though then form silver that the reduction of silver ion produces bunch as incipient nucleus, the essential lot of energy of karyogenesis can't easily form incipient nucleus.For this reason, the quantity of incipient nucleus reduces, and count and also reduce in the aggegation center of primary particle, so be difficult to obtain small fine silver particle.
【0059】
For example, when adding hydroquinone solution reduction silver ion in the liquor argenti nitratis ophthalmicus that adds ammoniacal liquor, the number of the preferred Nano silver grain of addition of Nano silver grain is 5.0 * 10 with the ratio of the number of silver ion -7～1.5 * 10 -In the scope of this addition, for example use the above liquor argenti nitratis ophthalmicus of silver concentration 50g/L, can be with the fine silver particle below the acquisition of the yield more than the 99% average grain diameter 1.5 μ m.
【0060】
In addition, in the manufacture method of the fine silver particle of the 3rd embodiment,, can control the particle diameter of the fine silver particle of separating out by adjusting addition with respect to the Nano silver grain of silver concentration.For example, when interpolation hydroquinone solution reduction silver ion is separated out small fine silver particle in the liquor argenti nitratis ophthalmicus that adds ammoniacal liquor, number by the Nano silver grain in the following adjustment solution can obtain the fine silver particle of average grain diameter 1.5～0.02 μ m with respect to the ratio (hereinafter referred to as Nano silver grain silver ion ratio) of the number of silver ion.
【0061】
(i) Nano silver grain silver ion ratio is adjusted into 5.0 * 10 -7～3.0 * 10 -6, separate out the fine silver particle of average grain diameter 1.5～0.5 μ m.
(ii) Nano silver grain silver ion ratio is adjusted into greater than 3.0 * 10 -6Smaller or equal to 2.5 * 10 -5, separate out the fine silver particle of average grain diameter 0.5～0.1 μ m.
(iii) Nano silver grain silver ion ratio is adjusted into greater than 2.5 * 10 -5Smaller or equal to 1.5 * 10 -4, separate out the fine silver particle of average grain diameter 0.1～0.02 μ m.
【0062】
(the 4th embodiment)
The manufacture method of the fine silver particle of the 4th embodiment has in silver ion solution adds the operation that ammonia and reducing agent reduction silver ion are separated out small fine silver particle, by after adding ammonia 20 seconds with interior interpolation reducing agent, small fine silver particle is separated out.
【0063】
Can use liquor argenti nitratis ophthalmicus etc. as silver ion solution.If in liquor argenti nitratis ophthalmicus, add ammonia, then form silver-colored amine complex, by silver is separated out in its reduction.Can use hydroquinone solution (OH (C as reducing agent 6H 4) OH, below be called for short H sometimes 2Q) etc.The not residual amount that does not form the silver ion of amine complex in the addition preferred solution of ammonia, its amount is that ammonia is 2～3 moles amount with respect to 1 mole of silver.The amount of the silver-colored amine complex of remained unreacted not in the addition preferred solution of reducing agent, its amount be for when reducing agent uses quinhydrones, is 0.3～1.0 mole amount with respect to silver-colored 1 mole of hydroquinone.
【0064】
The manufacture method of the fine silver particle of the 4th embodiment is to add behind the ammonia 20 seconds with interior interpolation reducing agent in silver ion solution.By adding reducing agent in the short time after adding ammonia, form the silver hydroxide (AgOH) or the silver oxide (Ag that generate for the moment before the silver-colored amine complex 2O) becoming karyomorphism becomes material and forms nuclear.Be the crystallinity primary particle of karyomorphism Cheng Yin with silver hydroxide or silver oxide then, aggegation forms fine silver particle between this primary particle.If after adding ammonia in 20 seconds, it is a large amount of residual and become nuclear then not form the silver hydroxide of amine complex or silver oxide.Therefore, the situation that generates silver bunch nuclear with the reduction silver ion is compared, and can increase the quantity of incipient nucleus, counts in the aggegation center that also can increase primary particle, therefore becomes for example following small fine silver particle of average grain diameter 2.5 μ m.On the other hand, if through being longer than when adding behind the ammonia 20 seconds, initial silver hydroxide and the silver oxide that generates becomes silver-colored amine complex, and can not form with silver hydroxide and silver oxide is the crystallinity primary particle of incipient nucleus.The generation number of the incipient nucleus of the silver bunch nuclear that the reduction of silver ion produces is few, and the aggegation center of primary particle is counted also few, therefore is difficult to obtain small fine silver particle.
【0065】
In the manufacture method of the fine silver particle of the 4th embodiment, in silver ion solution, add behind the ammonia 20 seconds, therefore do not adopt and in silver ion solution, add ammonia in advance and form silver-colored amine complex, perhaps in silver ion solution, add earlier reducing agent with interior interpolation reducing agent.
【0066】
In the manufacture method of the fine silver particle of the 4th embodiment, after adding ammonia 20 seconds with interior scope in, adjust by adding behind the ammonia to the elapsed time of adding reducing agent, can control the particle diameter of the fine silver particle of separating out thus.Particularly, can control the particle diameter of fine silver particle the following adjustment elapsed time.
【0067】
(i) by the above-mentioned elapsed time is adjusted into 0.3 second～in 0.5 second, the fine silver particle of average grain diameter 0.2 μ m～0.5 μ m is separated out.
(ii) be longer than 0.5 second and be in 2 seconds, the fine silver particle of average grain diameter 0.5 μ m～1.5 μ m is separated out by the above-mentioned elapsed time is adjusted into.
(iii) be longer than 2 seconds and be in 5 seconds, the fine silver particle of average grain diameter 1.5 μ m～2.0 μ m is separated out by the above-mentioned elapsed time is adjusted into.
(iv) be longer than 5 seconds and be in 20 seconds, the fine silver particle of average grain diameter 2.0 μ m～2.5 μ m is separated out by the above-mentioned elapsed time is adjusted into.
【0068】
The manufacturing installation of the fine silver particle of present embodiment is for adding the manufacturing installation that ammonia and reducing agent reduction silver ion are separated out fine silver particle in silver ion solution.This manufacturing installation one for example shown in Figure 24.As shown in the figure, the manufacturing installation of the fine silver particle of present embodiment has: the 2nd pipeline 14, reduction liquid bath 12, the end that the 1st pipeline 13, ammonia spirit groove 11, the end that silver ion solution groove 10, an end connect silver ion solution groove 10 connects ammonia spirit groove 11 connects the 3rd pipeline 15 of reduction liquid bath 12 and the 4th pipeline 16 that is extended out by the portion of reporting to the leadship after accomplishing a task of the 1st pipeline and the 2nd pipeline.The peristome of end that the 4th pipeline 16 and the 3rd pipeline 15 are set to the other end of its pipeline leaves mutually a little and is relative.
【0069】
During said apparatus constituted, silver ion was flowed by the other end of silver ion solution groove 10 to the 1st pipeline 13.Ammonia spirit is flowed by the other end of ammonia spirit groove 11 to the 2nd pipeline 14.Reducing solution is flowed by the other end of reduction liquid bath 12 to the 3rd pipeline 15.In the portion of reporting to the leadship after accomplishing a task of the 1st pipeline 13 and the 2nd pipeline 14, silver ion solution and ammonia spirit mix.This portion of reporting to the leadship after accomplishing a task is the hybrid position A of silver ion solution and ammonia spirit.By the peristome ejection silver ion solution of the end separately of the 4th pipeline 16 and the 3rd pipeline 15 and the mixed liquor and the reducing solution of ammonia spirit, mixing crosses in the outside of pipeline.Between the peristome of the end of the 4th pipeline 16 and the 3rd pipeline 15 mixed liquor of silver ion solution and ammonia spirit and the hybrid position B of reducing solution.
【0070】
The silver ion solution that is flowed out by silver ion solution groove 10 at first mixes with ammonia spirit with the portion of reporting to the leadship after accomplishing a task (hybrid position A) of the 2nd pipeline 14 at the 1st pipeline 13.Then, the mixed liquor of silver ion solution and ammonia spirit flows to the end of the other end of the 4th pipeline 16, is sprayed to the outside by the peristome of the end of the other end.The mixed liquor of silver ion solution and ammonia spirit, with reducing solution by the peristome ejection of the end of the other end of the 3rd pipeline 15, the mixing that crosses of the hybrid position B in the outside of pipeline.Add behind the ammonia to the time of adding reducing solution, according to deciding to long (flow path length) L of the pipeline of hybrid position B (pipeline by the distance of the other end of the portion to the of reporting to the leadship after accomplishing a task 4 pipelines 16 of the 1st pipeline 13 and the 2nd pipeline 14 or the 4th pipeline 16 is long), set long (flow path length) L of pipeline in the mode of interior interpolation reducing solution to add behind the ammonia 20 seconds by hybrid position A.
【0071】
The mixed liquor catch tank that the mixed liquor that hybrid position B place is mixed for example is arranged at the bottom of hybrid position B captures.Filter the mixed liquor that is captured then, obtain fine silver particle.
【0072】
During said apparatus constituted, the 4th pipeline 16 that hybrid position B is set was relative so that the peristome of the end of its pipeline leaves mutually a little with the 3rd pipeline 15.The peristome of the end of pipeline is oppositely arranged with leaving mutually, thus the silver ion solution of the interpolation ammonia that flows by the 4th pipeline 16, with mix in the outside of pipeline by the mobile reducing solution of the 3rd pipeline 15, the open space formation fine silver particle outside pipeline separate out the place.Therefore, do not adhere to fine silver particle, can not produce the thick problem of peeling off particle of sneaking into, therefore can obtain the fine silver particle of uniform particle diameter at pipeline inner wall.
【0073】
It should be noted that, by forming the portion of reporting to the leadship after accomplishing a task (hybrid position A) of the 1st pipeline 13 and the 2nd pipeline 14 movably, perhaps telescopically forms by the pipeline (4th pipeline 16) of hybrid position A to hybrid position B, can form adjustably by hybrid position A to long (flow path length) L of the pipeline of hybrid position B, can adjust by adding behind the ammonia to the elapsed time of adding reducing solution.
The other end that can be the 4th pipeline 16 in addition links to each other with the other end of the 3rd pipeline 15, a part of opening of the portion of reporting to the leadship after accomplishing a task, and mixed liquor is by constituting that peristome promptly sprays outside pipeline.At this moment, the coupling part of the 4th pipeline 16 and the 3rd pipeline 15 is the hybrid position B of silver ion solution and reducing solution.
[embodiment]
【0074】
Followingly specifically describe the present invention according to embodiment.The mensuration that it should be noted that particle diameter is tried to achieve with the calculation of number benchmark by laser light scattering/diffraction approach.
【0075】
(embodiment 1)
In the liquor argenti nitratis ophthalmicus that adds ammoniacal liquor, added the hydroquinone solution of ammonium iodide solution, the reduction silver ion is separated out fine silver particle.The composition of ammoniacal liquor, liquor argenti nitratis ophthalmicus, hydroquinone solution is shown in table 1.In addition, use amount, the iodine with ammonium iodide solution is shown in table 2 with respect to the mol ratio of silver.Average grain diameter, yield, the iodine amount of the fine silver particle of separating out are shown in table 2.And then, for the part sample, the SEM photo of particle is shown in Fig. 3～Fig. 6.It should be noted that in the table 2 that Sample A 1～A11 is a sample of the present invention.To not add the 1a of sample as a comparison of ammonium iodide solution, will be than the excessive example of iodine addition preferred range sample 1b as a comparison.The atomic particle diameter control of Ag expression is with respect to the mobility scale [μ m] of average grain diameter, and yield is represented with percentage [%].NH 4The I concentration of aqueous solution is 0.02% in Sample A 1～Sample A 7, is 2% among Sample A 8～Sample A 11 and the duplicate 1b.In addition, will change with respect to the average grain diameter of the fine silver particle of the addition of iodine and be shown in Fig. 1.Horizontal line about shown in the measured value among the figure is represented the deviation range of the measured value of 10 tests.
【0076】
[table 1]
Figure A20088000695600251
【0077】
[table 2]
Figure A20088000695600252
【0078】
As table 2 and shown in Figure 1, do not add in the duplicate of ammonium iodide, separate out the above fine silver particle of average grain diameter 1.5 μ m, if but have iodide ion, then fine silver particle becomes small, and the average grain diameter of fine silver particle is according to the iodide ion quantitative changeization.Particularly, (i) iodine silver mol ratio (I/Ag) 5.0 * 10 -8～1.8 * 10 -6Scope the time, the fine silver particle of average grain diameter 1.5～0.5 μ m is separated out, (ii) iodine silver mol ratio is greater than 1.8 * 10 -6Smaller or equal to 3.0 * 10 -5Scope the time, the fine silver particle of average grain diameter 0.5～0.15 μ m is separated out, (iii) iodine silver mol ratio is greater than 3.0 * 10 -5Smaller or equal to 1.5 * 10 -3Scope the time, the fine silver particle of average grain diameter 0.15～0.08 μ m is separated out.
【0079】
In addition, as table 2 and shown in Figure 1, the particle diameter of fine silver particle of the present invention controlled good, the particle diameter of the fine silver particle of embodiment is all in-10%～10% scope of average grain diameter that 10 tests are tried to achieve (the particle diameter control of table 2).And then the ageing stability excellence of the soup that the present invention uses is modulated the back 9 hours particle diameters with interior synthetic fine silver particle also in-10%～10% scope.
【0080】
(embodiment 2)
In the liquor argenti nitratis ophthalmicus that adds ammoniacal liquor, add hydroquinone solution (the halid molal quantity: 2.82 * 10 that adds ammonium halide solution in advance -5), the reduction silver ion is separated out fine silver particle.Liquor argenti nitratis ophthalmicus, hydroquinone solution, ammonium salt solution use the solution shown in the table 1.The kind of halogen is as shown in table 3, uses NH 4Cl, NH 4Br, NH 4I.The average grain diameter of the fine silver particle that mensuration is separated out.The assay method of average grain diameter is identical with embodiment 1.The results are shown in table 3 and Fig. 7～Figure 10.It should be noted that in the table 3 that sample B 1～sample B 3 is sample of the present invention.Ammonium halide solution person sample 2 as a comparison will do not added.Halide salt aqueous solution is the 0.1M aqueous solution, and silver-colored solution is identical with table 1 with reducing solution.As table 3 and Fig. 7～shown in Figure 10, strengthen according to the order of iodine, bromine, chlorine effect to the microminiaturization of silver particles.
【0081】
[table 3]
Duplicate 2 Sample B 1 Sample B 2 Sample B 3
The kind of halogen ?- ??NH 4Cl ??NH 4Br ??NH 4I
Liquid measure (μ L) ?0 ??300 ??300 ??300
Halogen quantity (g) ?0 ??1.06×10 -3 ??2.39×10 -3 ??3.80×10 -3
With Ag mol ratio (-) ?0 ??3.23×10 -5 ??3.23×10 -5 ??3.23×10 -5
Ag particle diameter (μ m) ?1.71 ??0.40 ??0.20 ??0.12
The SEM image Fig. 7 Fig. 8 Fig. 9 Figure 10
【0082】
(embodiment 3)
The ammonium halide solution that replaces embodiment 2 uses the halide salt aqueous solution shown in the table 4, in addition with the condition reduction silver ion identical with embodiment 2 fine silver particle is separated out, and measures the average grain diameter of the fine silver particle of separating out.The assay method of average grain diameter is identical with embodiment 1.The results are shown in table 4.It should be noted that in the table 4 that sample C1～sample C3 is a sample of the present invention.The sample as a comparison 3 of the halide salt aqueous solution will do not added.In addition, halide salt aqueous solution is the 0.1M aqueous solution, and silver-colored solution is identical with table 1 with reducing solution.As shown in table 4, even the counter ion counterionsl gegenions of halide ion change, effect of the present invention is also constant.
【0083】
[table 4]
Figure A20088000695600271
【0084】
(comparative example 1)
Use the liquor argenti nitratis ophthalmicus of the adding ammoniacal liquor shown in table 5 (duplicate 4) and the table 6 (duplicate 5), add hydroquinone solution in this solution, the reduction silver ion is separated out fine silver particle, measures the average grain diameter of the fine silver particle of separating out.The assay method of average grain diameter is identical with embodiment 1.The results are shown in table 7.Do not add in advance in reducing solution under the situation of halide ion, can obtain average grain diameter by the dilution silver concentration is fine silver particle below the 0.50 μ m, but yield is lower than 99% owing to be difficult to reclaim.
【0085】
[table 5]
Figure A20088000695600281
【0086】
[table 6]
Figure A20088000695600282
【0087】
[table 7]
Duplicate 4 Duplicate 5
Ag particle diameter (μ m) ??0.35 ??0.47
Yield (%) ??96.7 ??97.9
【0088】
(embodiment 4)
Use the liquor argenti nitratis ophthalmicus of adding ammoniacal liquor as shown in table 8, use hydroquinone solution, use hydrazine solution as main reducing agent as secondary reducing agent A, the hydroquinone solution that is added with secondary reductant solution is in advance added liquor argenti nitratis ophthalmicus, and the reduction silver ion is separated out fine silver particle.The addition of secondary reductant solution is adjusted into the concentration shown in the table 9, measures the average grain diameter of the fine silver particle of separating out by laser-scattering/diffraction approach.With the table 9 that the results are shown in that obtains.It should be noted that in the table 9 that sample D1～D11 is a sample of the present invention, will not add the sample as a comparison of secondary reducing agent.In the state of fine silver particle, represent not have the situation of aggegation, represent to have the situation of aggegation with NG with OK.In addition, will be shown in Figure 11 with respect to the variation of the average grain diameter of the fine silver particle of the addition of hydrazine.Horizontal line up and down shown in the measured value among the figure is represented the deviation range of the measured value of 10 tests.For the part sample, the electron micrograph of representing particle state is shown in Figure 13～Figure 17.
【0089】
[table 8]
【0090】
[table 9]
Figure A20088000695600292
Figure A20088000695600301
【0091】
(embodiment 5～embodiment 6)
Use sodium borohydride solution (embodiment 5) or use boron hydride dimethyl amine solution (embodiment 6) as secondary reducing agent C as secondary reducing agent B, other are identical with embodiment 4, make fine silver particle.The results are shown in table 10 (embodiment 5:E1～E3), table 11 (embodiment 6:F1～F3).The relation of secondary reducing agent addition and Ag particle diameter has been shown among Figure 12 in addition.
【0092】
[table 10]
??NaBH 4Amount (g) The ratio of secondary reducing agent silver Ag particle diameter (μ m) Ag yield (%) Remarks
Sample E1 ??7.01×10 -5 ??2.00×10 -6 ??0.99 ??＞99 No aggegation
Sample E2 ??7.01×10 -3 ??2.00×10 -4 ??0.34 ??＞99 No aggegation
Sample E3 ??7.01×10 -1 ??2.00×10 -2 ??0.12 ??＞99 No aggegation
【0093】
[table 11]
??BH 3·HN(CH 3) 2Amount (g) The ratio of secondary reducing agent silver Ag particle diameter (μ m) Ag yield (%) Remarks
Sample F1 ??1.09×10 -4 ??2.00×10 -6 ??1.10 ??＞99 No aggegation
Sample F2 ??1.09×10 -2 ??2.00×10 -4 ??0.40 ??＞99 No aggegation
Sample F3 ??1.09×10 0 ??2.00×10 -2 ??0.15 ??＞99 No aggegation
【0094】
As table 9～table 11 and Figure 11～shown in Figure 12, do not add in the comparison of secondary reducing agent, the above fine silver particle of average grain diameter 1.8 μ m is separated out, if but add secondary reducing agent, then fine silver particle becomes small, and the average grain diameter of fine silver particle changes according to the addition of secondary reducing agent.Particularly, (i) hydrazine silver compares 2.5 * 10 -7～3.0 * 10 -5Scope the time average grain diameter 1.5～0.5 μ m fine silver particle separate out, (ii) hydrazine silver is than greater than 3.0 * 10 -5Smaller or equal to 4.2 * 10 -2Scope the time average grain diameter 0.5～0.1 μ m fine silver particle separate out, (iii) hydrazine silver is than greater than 4.2 * 10 -2Smaller or equal to 5.0 * 10 -1Scope the time average grain diameter 0.1～0.05 μ m fine silver particle separate out.
【0095】
In addition, as shown in figure 11, the particle diameter of fine silver particle of the present invention controlled good, the particle diameter of the fine silver particle of embodiment all-20%～20% with interior scope in.And then, the ageing stability excellence of soup of modulation according to the present invention, modulate back 3 hours with the particle diameter of interior synthetic fine silver particle also-20%～20% with interior scope in.
【0096】
(comparative example 2)
Use the liquor argenti nitratis ophthalmicus of the adding ammoniacal liquor shown in table 12 (duplicate 11) and table 13 (duplicate 12), add hydroquinone solution in this solution, the reduction silver ion is separated out fine silver particle, measures the average grain diameter of the fine silver particle of separating out.The assay method of average grain diameter is identical with embodiment 4.The results are shown in table 14.In the situation of not adding secondary reducing agent, can obtain average grain diameter by the dilution silver concentration is fine silver particle below the 0.50 μ m, but yield is lower than 99% owing to be difficult to reclaim.
【0097】
[table 12]
Figure A20088000695600311
【0098】
[table 13]
Figure A20088000695600312
【0099】
[table 14]
Duplicate 11 Duplicate 12
Ag particle diameter (μ m) ??0.35 ??0.47
Yield (%) ??96.7 ??97.9
【0100】
(embodiment 7)
Use the liquor argenti nitratis ophthalmicus of adding ammoniacal liquor as shown in Table 15, add Nano silver grain in advance in this solution, and then add hydroquinone solution, the reduction silver ion is separated out fine silver particle.The particle footpath and the addition of Nano silver grain are adjusted into the condition shown in table 16～table 17.The average grain diameter of the fine silver particle of separating out according to laser-scattering method.Observe fine silver particle by SEM.The results are shown in table 16～table 17 and Figure 18～Figure 23 with what obtain.It should be noted that sample G1～G5, H1～H3, J1～J3, K are sample of the present invention, will not add the sample as a comparison of Nano silver grain.
【0101】
As table 16～table 17 and Figure 18～shown in Figure 23, in the comparative example that does not add Nano silver grain, the above fine silver particle of average grain diameter 1.5 μ m is separated out, if but add Nano silver grain, then the average grain diameter of fine silver particle changes according to the particle footpath and the addition of Nano silver grain.Particularly, (i) Nano silver grain silver ion ratio is 5.0 * 10 -7～3.0 * 10 -6Scope the time, the fine silver particle of average grain diameter 1.5～0.5 μ m is separated out.In addition, (ii) Nano silver grain silver ion ratio greater than 3.0 * 10 -6Smaller or equal to 2.5 * 10 -5Scope the time, the fine silver particle of average grain diameter 0.5～0.1 μ m is separated out.In addition, (iii) Nano silver grain silver ion ratio greater than 2.5 * 10 -5Smaller or equal to 1.5 * 10 -4Scope the time, the fine silver particle of average grain diameter 0.1～0.02 μ m is separated out.It should be noted that among sample G～J, use the Nano silver grain of citric acid method preparation, among the sample K, use the Nano silver grain of the 50nm of method for making not quite clear (non-opening shown).
【0102】
[table 15]
Figure A20088000695600331
【0103】
[table 16]
Nano particle footpath (nm) The Nano silver grain silver ion is than (-) Ag particle diameter (μ m) Ag yield (%) Remarks
Duplicate 13 Do not have One ??1.67 ??＞99 Figure 20
Duplicate 14 ??5 ??9.38×10 -8 ??1.67 ??＞99
Duplicate 15 ??5 ??2.11×10 -7 ??1.66 ??＞99
Sample G1 ??5 ??4.93×10 -7 ??1.55 ??＞99 Figure 21
Sample G2 ??5 ??3.17×10 -6 ??0.47 ??＞99 Figure 22
Sample G3 ??5 ??6.80×10 -6 ??0.27 ??＞99 Figure 23
Sample G4 ??5 ??2.70×10 -5 ??0.09 ??＞99
Sample G5 ??5 ??1.50×10 -4 ??0.02 ??＞99
Duplicate 16 ??5 ??3.50×10 -4 ??0.02 ??＞99 The abnormity powder
【0104】
[table 17]
Nano particle footpath (nm) The Nano silver grain silver ion is than (-) Ag particle diameter (μ m) Ag yield (%) Remarks
Sample H1 ??2.6 ??8.34×10 -7 ??1.15 ??＞99
Sample H2 ??2.6 ??3.34×10 -6 ??0.45 ??＞99
Sample H3 ??2.6 ??2.42×10 -5 ??0.09 ??＞99
Sample J1 ??16.4 ??9.31×10 -7 ??1.50 ??＞99
Sample J2 ??16.4 ??2.66×10 -6 ??0.65 ??＞99
Sample J3 ??16.4 ??1.33×10 -5 ??0.15 ??＞99
Sample K ??50.0 ??7.04×10 -7 ??1.50 ??＞99
【0105】
(comparative example 3)
Use the liquor argenti nitratis ophthalmicus of the adding ammoniacal liquor shown in table 18 (duplicate 17) and table 19 (duplicate 18), add hydroquinone solution in this solution, the reduction silver ion is separated out fine silver particle, measures the average grain diameter of the fine silver particle of separating out.The assay method of average grain diameter is identical with embodiment 1.The results are shown in table 20.Under the situation of not adding Nano silver grain, by the dilution silver concentration, also can obtain average grain diameter is the following fine silver particle of 0.50 μ m, but yield is lower than 99% owing to be difficult to reclaim.
【0106】
[table 18]
Figure A20088000695600341
【0107】
[table 19]
Figure A20088000695600351
【0108】
[table 20]
Duplicate 17 Duplicate 18
Ag particle diameter (μ m) ??0.35 ??0.47
Yield (%) ??96.7 ??97.9
【0109】
(embodiment 8 and comparative example 4)
Use liquor argenti nitratis ophthalmicus (AgNO shown in table 21 3Solution) and ammoniacal liquor (NH 3Water), use hydroquinone solution (OH (C as reducing agent 6H 4) OH liquid), on one side ammoniacal liquor is remained in mixed weight than 8.0～8.2, the silver ion that reduces is separated out fine silver particle with interior interpolation reducing agent to add behind the ammoniacal liquor 20 seconds on one side in liquor argenti nitratis ophthalmicus.Adjust the elapsed time of adding till the reducing solution shown in table 22ly.The average grain diameter of the fine silver particle of separating out according to laser-scattering method.
【0110】
The table 22 that the results are shown in sample L1～L7 of the present invention.The table 23 that the results are shown in duplicate M1～M5.The relation of adding in liquor argenti nitratis ophthalmicus behind the ammoniacal liquor up to the particle diameter of elapsed time of adding reducing agent and silver particles is shown in Figure 25.The electron micrograph of the particle state of the silver particles of expression sample L1～L5 is shown in Figure 26～Figure 30.
【0111】
As table 22 and shown in Figure 25, (i) the above-mentioned elapsed time is in 0.3 second～0.5 second the time, and the fine silver particle of average grain diameter 0.2 μ m～0.5 μ m is separated out.The (ii) above-mentioned elapsed time was longer than 0.5 second and was in 2 seconds the time, and the fine silver particle of average grain diameter 0.5 μ m～1.5 μ m is separated out.The (iii) above-mentioned elapsed time was longer than 2 seconds and was in 5 seconds the time, and the fine silver particle of average grain diameter 1.5 μ m～2.0 μ m is separated out.The (iv) above-mentioned elapsed time was longer than 5 seconds and was in 20 seconds the time, and the fine silver particle of average grain diameter 2.0 μ m～2.5 μ m is separated out.
【0112】
[table 21]
Figure A20088000695600361
【0113】
[table 22]
Sample L1 Sample L2 Sample L3 Sample L4 Sample L5 Sample L6 Sample L7
Elapsed time (second) ??0.3 ??0.5 ??1.4 ??3 ??6 ??10 ??20
Ag particle diameter (μ m) ??0.21 ??0.47 ??1.13 ??1.73 ??2.13 ??2.45 ??2.49
Ag yield (%) ??＞99 ??＞99 ??＞99 ??＞99 ??＞99 ??＞99 ??＞99
Remarks Figure 26 Figure 27 Figure 28 Figure 29 ??- ??- Figure 30
【0114】
[table 23]
Figure A20088000695600371
[industrial applicability]
【0115】
According to manufacture method and the manufacturing installation of fine silver particle of the present invention, the small silver particles of excellent dispersion of the present invention can be stablized and be made efficiently to the silver ion solution of use high concentration. For this reason, fine silver particle of the present invention is applicable to the thickener composition of the wiring material that becomes electronic device or electrode material, and the manufacture method of fine silver particle of the present invention and manufacturing installation are applicable to the manufacturing process of this silver particles in addition.

Claims (26)

1. fine silver particle is characterized in that, in fine silver particle with respect to silver, with 5.0 * 10 -8～1.5 * 10 -3Mol ratio contain halogen.
2. fine silver particle as claimed in claim 1, wherein, with respect to aforementioned silver with 5.0 * 10 -8～1.8 * 10 -6Mol ratio contain aforementioned halogen, average grain diameter is 1.5～0.5 μ m.
3. fine silver particle as claimed in claim 1, wherein, with respect to aforementioned silver with greater than 1.8 * 10 -6Smaller or equal to 3.0 * 10 -5Mol ratio contain aforementioned halogen, average grain diameter is 0.5～0.15 μ m.
4. fine silver particle as claimed in claim 1, wherein, with respect to aforementioned silver with greater than 3.0 * 10 -5Smaller or equal to 1.5 * 10 -3Mol ratio contain aforementioned halogen, average grain diameter is 0.15～0.08 μ m.
5. the manufacture method of fine silver particle is characterized in that, have in silver ion solution, to add reducing agent, and reduction silver ion and operation that fine silver particle is separated out,
By the karyomorphism at the nuclear that becomes aforementioned fine silver particle become material in the presence of reduce silver ion, aforementioned fine silver particle is separated out.
6. the manufacture method of fine silver particle as claimed in claim 5 wherein, by the aforementioned silver ion of reduction in the presence of halide ion, makes silver halide become material to generate as aforementioned karyomorphism, and aforementioned fine silver particle is separated out.
7. the manufacture method of fine silver particle as claimed in claim 6 wherein, by adjusting the halide concentration with respect to silver concentration, is controlled the particle diameter of the aforementioned fine silver particle of separating out.
8. the manufacture method of fine silver particle as claimed in claim 7.Wherein, use the liquor argenti nitratis ophthalmicus that adds ammoniacal liquor, use hydroquinone solution,, use ammonium chloride (NH as compound with aforementioned halide ion as aforementioned reducing agent as aforementioned silver ion solution 4Cl), ammonium bromide (NH 4Br), ammonium iodide (NH 4I), potassium chloride (KCl), KBr (KBr), KI (KI), sodium chloride (NaCl), sodium bromide (NaBr) or sodium iodide (NaI).
9. the manufacture method of fine silver particle as claimed in claim 6 wherein, is used iodide ion as aforementioned halide ion, when reducing aforementioned silver ion, (i) iodine is adjusted into 5.0 * 10 with respect to the mol ratio (iodine silver mol ratio, I/Ag) of silver -8～1.8 * 10 -6The fine silver particle of average grain diameter 1.5～0.5 μ m is separated out, perhaps (ii) aforementioned iodine silver mol ratio is adjusted into greater than 1.8 * 10 -6Smaller or equal to 3.0 * 10 -5The fine silver particle of average grain diameter 0.5～0.15 μ m is separated out, perhaps (iii) aforementioned iodine silver mol ratio is adjusted into greater than 3.0 * 10 -5Smaller or equal to 1.5 * 10-3 the fine silver particle of average grain diameter 0.15～0.08 μ m is separated out.
10. the manufacture method of fine silver particle as claimed in claim 6, wherein, as aforementioned silver ion solution, use the above liquor argenti nitratis ophthalmicus of silver concentration 50g/L that adds ammoniacal liquor, use hydroquinone solution as aforementioned reducing agent, use iodide ion as aforementioned halide ion, by iodine is adjusted into 5.0 * 10 with respect to the mol ratio (I/Ag) of silver -8～1.5 * 10 -3, the yield that makes the fine silver particle of average grain diameter 1.5～0.08 μ m is more than 99%.
11. the manufacture method of fine silver particle as claimed in claim 5, wherein, unite and use main reducing agent and the secondary reducing agent stronger than main reducing agent reducing power, in aforementioned silver ion solution, in the presence of a spot of aforementioned auxiliary reducing agent, add aforementioned main reducing agent, the aforementioned silver ion of reduction in the presence of this main reducing agent and secondary reducing agent, make the fine silver particle of colloid shape become material to generate thus, aforementioned fine silver particle is separated out as aforementioned karyomorphism.
12. the manufacture method of fine silver particle as claimed in claim 11, wherein, by adjusting the addition of aforementioned auxiliary reducing agent, the particle diameter of the aforementioned fine silver particle that control is separated out.
13. the manufacture method of fine silver particle as claimed in claim 11 wherein, is controlled in 2.5 * 10 with secondary reducing agent with respect to the mol ratio (ratio of secondary reducing agent silver) of silver concentration -7～5.0 * 10 -1, the fine silver particle of average grain diameter 1.5～0.05 μ m is separated out.
14. the manufacture method of fine silver particle as claimed in claim 13, wherein, (i) ratio with aforementioned auxiliary reducing agent silver is adjusted into 2.5 * 10 -7～3.0 * 10 -5The fine silver particle of average grain diameter 1.5～0.5 μ m is separated out, perhaps (ii) the ratio of aforementioned auxiliary reducing agent silver is adjusted into greater than 3.0 * 10 -5Smaller or equal to 4.2 * 10 -2The fine silver particle of average grain diameter 0.5～0.1 μ m is separated out, perhaps (iii) the ratio of aforementioned auxiliary reducing agent silver is adjusted into greater than 4.2 * 10 -2Smaller or equal to 5.0 * 10 -1The fine silver particle of average grain diameter 0.1～0.05 μ m is separated out.
15. the manufacture method of fine silver particle as claimed in claim 11 wherein, is used the liquor argenti nitratis ophthalmicus that adds ammoniacal liquor as aforementioned silver ion solution, uses hydroquinone solution as aforementioned main reducing agent, uses hydrazine as the aforementioned auxiliary reducing agent.
16. the manufacture method of fine silver particle as claimed in claim 11, wherein, use mixed with little amount in the hydroquinone solution of aforementioned main reducing agent has the solution of the hydrazine solution of aforementioned auxiliary reducing agent, after perhaps in aforementioned silver ion solution, adding the hydrazine solution of a small amount of aforementioned auxiliary reducing agent, the hydroquinone solution of adding aforementioned main reducing agent immediately.
17. the manufacture method of fine silver particle as claimed in claim 5 wherein, is added Nano silver grain and become material as aforementioned karyomorphism in aforementioned silver ion solution, the aforementioned silver ion of reduction makes aforementioned fine silver particle separate out thus in the presence of this Nano silver grain.
18. the manufacture method of fine silver particle as claimed in claim 17, wherein, by adjusting the addition of aforementioned Nano silver grain, the particle diameter of the aforementioned fine silver particle that control is separated out with respect to silver concentration.
19. the manufacture method of fine silver particle as claimed in claim 17 wherein, is used the liquor argenti nitratis ophthalmicus that adds ammoniacal liquor as aforementioned silver ion solution, uses hydroquinone solution as aforementioned reducing agent, adds the following Nano silver grain of average grain diameter 50nm.
20. the manufacture method of fine silver particle as claimed in claim 17, wherein the ratio of the number of (i) silver ion that the number of aforementioned Nano silver grain is contained with respect to aforementioned silver ion solution (Nano silver grain silver ion than) is adjusted into 5.0 * 10 -7～3.0 * 10 -6The fine silver particle of average grain diameter 1.5～0.5 μ m is separated out, perhaps (ii) aforementioned Nano silver grain silver ion ratio is adjusted into greater than 3.0 * 10 -6Smaller or equal to 2.5 * 10 -5The fine silver particle of average grain diameter 0.5～0.1 μ m is separated out, perhaps (iii) aforementioned Nano silver grain silver ion ratio is adjusted into greater than 2.5 * 10 -5Smaller or equal to 1.5 * 10 -4The fine silver particle of average grain diameter 0.1～0.02 μ m is separated out.
21. the manufacture method of fine silver particle as claimed in claim 17, wherein, as aforementioned Nano silver grain, use the Nano silver grain below the average grain diameter 20nm that in the presence of natrium citricum, in liquor argenti nitratis ophthalmicus, adds ferrous sulfate reduction silver ion and generate.
22. the manufacture method of fine silver particle as claimed in claim 5, wherein, in aforementioned silver ion solution, add ammonia, add behind the aforementioned ammonia 20 seconds with the aforementioned reducing agent of interior interpolation, make silver hydroxide or silver oxide become material to generate thus, aforementioned fine silver particle is separated out as aforementioned karyomorphism.
23. the manufacture method of fine silver particle as claimed in claim 22, wherein, by adjusting from the time of the interpolation that is added into aforementioned reducing agent of aforementioned ammonia the particle diameter of the fine silver particle that control is separated out.
24. the manufacture method of fine silver particle as claimed in claim 22, wherein, for (i) making the aforementioned elapsed time from time (elapsed time) of the interpolation that is added into aforementioned reducing agent of aforementioned ammonia is to separate out with the interior fine silver particle of average grain diameter 0.2～0.5 μ m that makes in 0.3～0.5 second, the aforementioned elapsed time was longer than 0.5 second and is to separate out with the interior fine silver particle of average grain diameter 0.5 μ m～1.5 μ m that makes in 2 seconds, the aforementioned elapsed time was longer than 2 seconds and is to separate out with the interior fine silver particle of average grain diameter 1.5 μ m～2.0 μ m that makes in 5 seconds, the aforementioned elapsed time was longer than 5 seconds and is to separate out with the interior fine silver particle of average grain diameter 2.0 μ m～2.5 μ m that makes in 20 seconds.
25. the manufacturing installation of fine silver particle, it is for adding the manufacturing installation that ammonia and reducing agent reduction silver ion are separated out fine silver particle in silver ion solution, it is characterized in that, have: the silver ion solution groove, be connected in the 1st pipeline of aforementioned silver ion solution groove, the ammonia spirit groove, be connected in the 2nd pipeline of aforementioned ammonia spirit groove, the reduction liquid bath, be connected in the 3rd pipeline of aforementioned reduction liquid bath, with the 4th pipeline that the portion of reporting to the leadship after accomplishing a task from aforementioned the 1st pipeline and aforementioned the 2nd pipeline extends out, make from the reducing solution of aforementioned the 3rd pipeline with mixed from the mixed liquor of the silver ion solution of aforementioned the 4th pipeline and ammonia solution.
26. the manufacturing installation of fine silver particle as claimed in claim 25, wherein, it is relative that the peristome that aforementioned the 3rd pipeline and aforementioned the 4th pipeline are set to the end of its pipeline leaves ground mutually a little, by the portion of reporting to the leadship after accomplishing a task of aforementioned the 1st pipeline and aforementioned the 2nd pipeline extremely the flow path length of the end of aforementioned the 4th pipeline be adjustable.
CN2008800069565A 2007-03-30 2008-03-31 Fine silver particle, process for producing fine silver particle, and apparatus for producing fine silver particle Active CN101626856B (en)

Applications Claiming Priority (9)

Application Number Priority Date Filing Date Title
JP095658/2007 2007-03-30
JP2007095659 2007-03-30
JP2007095657 2007-03-30
JP2007095658A JP2008255377A (en) 2007-03-30 2007-03-30 Method for producing silver particulate
JP2007095660A JP2008255378A (en) 2007-03-30 2007-03-30 Method for producing silver particulate
JP095659/2007 2007-03-30
JP095657/2007 2007-03-30
JP095660/2007 2007-03-30
PCT/JP2008/056319 WO2008123494A1 (en) 2007-03-30 2008-03-31 Fine silver particle, process for producing fine silver particle, and apparatus for producing fine silver particle

Publications (2)

Publication Number Publication Date
CN101626856A true CN101626856A (en) 2010-01-13
CN101626856B CN101626856B (en) 2012-10-10

Family

ID=40052744

Family Applications (1)

Application Number Title Priority Date Filing Date
CN2008800069565A Active CN101626856B (en) 2007-03-30 2008-03-31 Fine silver particle, process for producing fine silver particle, and apparatus for producing fine silver particle

Country Status (2)

Country Link
JP (1) JP5376109B2 (en)
CN (1) CN101626856B (en)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102699341A (en) * 2012-04-26 2012-10-03 蔡雄辉 Wet-chemical preparation method for silver micro/nanowires
CN103341643A (en) * 2013-07-26 2013-10-09 武汉理工大学 Preparation method of composite reducing agent liquid phase for conductive composite particles coated with silver shell layers
CN104010752A (en) * 2011-12-28 2014-08-27 户田工业株式会社 Silver fine particles, production process therefor, conductive paste, conductive membrane and electronic device, containing said silver fine particles
CN107297510A (en) * 2016-04-15 2017-10-27 中国科学院理化技术研究所 Method for preparing nano-scale silver particle powder by reducing silver salt intermediate in grading manner
CN107755711A (en) * 2017-10-20 2018-03-06 昆明理工大学 A kind of square micro-nano silver powder, preparation method thereof

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6417803A (en) * 1987-07-14 1989-01-20 Agency Ind Science Techn Method for coating metal fine powder with other metal
JPH10265812A (en) * 1997-03-24 1998-10-06 Sumitomo Metal Mining Co Ltd Production of superfine silver particle
JPH111733A (en) * 1997-06-06 1999-01-06 Sumitomo Metal Mining Co Ltd Ag-ni electric contact point material and its manufacture
JP4480884B2 (en) * 1999-12-22 2010-06-16 三井金属鉱業株式会社 Method for producing surface-modified silver powder
TWI243725B (en) * 2003-05-27 2005-11-21 Samsung Electronics Co Ltd Method for preparing non-magnetic nickel powders
JP2005325411A (en) * 2004-05-14 2005-11-24 Fukuda Metal Foil & Powder Co Ltd Metal powder having excellent sinterability, its production method and method for producing sintered compact using the metal powder

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104010752A (en) * 2011-12-28 2014-08-27 户田工业株式会社 Silver fine particles, production process therefor, conductive paste, conductive membrane and electronic device, containing said silver fine particles
CN102699341A (en) * 2012-04-26 2012-10-03 蔡雄辉 Wet-chemical preparation method for silver micro/nanowires
CN102699341B (en) * 2012-04-26 2015-09-23 蔡雄辉 A kind of wet chemical preparation method of silver-colored micro-/ nano line
CN103341643A (en) * 2013-07-26 2013-10-09 武汉理工大学 Preparation method of composite reducing agent liquid phase for conductive composite particles coated with silver shell layers
CN103341643B (en) * 2013-07-26 2015-09-30 武汉理工大学 The complex reducing agent liquid phase preparation process of coated with silver on surface shell conductive composite particle
CN107297510A (en) * 2016-04-15 2017-10-27 中国科学院理化技术研究所 Method for preparing nano-scale silver particle powder by reducing silver salt intermediate in grading manner
CN107297510B (en) * 2016-04-15 2019-06-14 中国科学院理化技术研究所 Method for preparing nano-scale silver particle powder by reducing silver salt intermediate in grading manner
CN107755711A (en) * 2017-10-20 2018-03-06 昆明理工大学 A kind of square micro-nano silver powder, preparation method thereof
CN107755711B (en) * 2017-10-20 2019-07-05 昆明理工大学 A kind of pros' micro-nano silver powder, preparation method thereof

Also Published As

Publication number Publication date
JP2008274423A (en) 2008-11-13
JP5376109B2 (en) 2013-12-25
CN101626856B (en) 2012-10-10

Similar Documents

Publication Publication Date Title
JP5355007B2 (en) Method for producing spherical silver powder
CN101626856B (en) Fine silver particle, process for producing fine silver particle, and apparatus for producing fine silver particle
US7648557B2 (en) Process for making highly dispersible spherical silver powder particles and silver particles formed therefrom
US8486310B2 (en) Composition containing fine silver particles, production method thereof, method for producing fine silver particles, and paste having fine silver particles
CN104411429B (en) The manufacture method of metal particle
CN101801568A (en) Process for producing copper powder and copper powder
JP2012526191A (en) Silver particles and method for producing the same
US8574338B2 (en) Reactor and continuous process for producing silver powders
CN101583449A (en) Silver fine powder, method for producing the same, and ink
JP2012525506A (en) Silver particles and method for producing the same
CN101495257B (en) Silver fine particles and processes and equipment for the production thereof
JP2011042839A (en) Method for producing silver powder and production device therefor
Soofivand et al. Simple and facile synthesis of Ag2CrO4 and Ag2Cr2O7 micro/nanostructures using a silver precursor
JP4496026B2 (en) Method for producing metallic copper fine particles
CN107186218B (en) A kind of preparation method of modified superfine noble metal powder
CN103079726A (en) Silver particles and a process for making them
CN113369491B (en) Spherical and flaky mixed silver powder and manufacturing method thereof
JP5224022B2 (en) Method and apparatus for producing silver fine particles
CN101954488A (en) Method for preparing zerovalent iron nanoparticles by improved liquid phase reduction method
CN104445358B (en) A kind of double-decker cuprous nano microsphere and preparation method thereof
CN104259479A (en) Preparation method of nanometer tin alloy powder for soldering paste
KR20150143359A (en) Method for fabricating hollow metal nano particles and hollow metal nano particles fabricated by the method
TWI468240B (en) Silver fine particles, method for manufacturing silver fine particles, and apparatus for manufacturing silver fine particles
Liu et al. A new type of capping agent in nanoscience: metal cations
JP2008255377A (en) Method for producing silver particulate

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant