CN101626856B - Fine silver particle, process for producing fine silver particle, and apparatus for producing fine silver particle - Google Patents

Fine silver particle, process for producing fine silver particle, and apparatus for producing fine silver particle Download PDF

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Publication number
CN101626856B
CN101626856B CN2008800069565A CN200880006956A CN101626856B CN 101626856 B CN101626856 B CN 101626856B CN 2008800069565 A CN2008800069565 A CN 2008800069565A CN 200880006956 A CN200880006956 A CN 200880006956A CN 101626856 B CN101626856 B CN 101626856B
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silver
particle
fine silver
aforementioned
fine
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CN101626856A (en
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樋上晃裕
宇野贵博
佐藤一祐
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Mitsubishi Materials Corp
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Mitsubishi Materials Corp
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Priority claimed from JP2007095658A external-priority patent/JP2008255377A/en
Priority claimed from JP2007095660A external-priority patent/JP2008255378A/en
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Priority claimed from PCT/JP2008/056319 external-priority patent/WO2008123494A1/en
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Abstract

Fine silver particles which contain a halogen in an amount of 5.0OE0-8 to 1.5OE0-3 mol per mol of the silver. Also provided is a process for producing the fine silver particles which includes a step in which a reducing agent is added to a silver ion solution to reduce the silver ions and thereby precipitate fine silver particles, the silver ion reduction being conducted in the presence of a nucleating substance which constitutes nuclei for the fine silver particles. Furthermore provided is an apparatus for producing the fine silver particles which comprises a silver ion solution tank, a first pipeline connected to the silver ion solution tank, an aqueous-ammonia-solution tank, a second pipeline connected to the aqueous-ammonia-solution tank, a reducing-liquid tank, a third pipeline connected to the reducing-liquid tank, and a fourth pipeline extending from a part where the first and second pipelines cross each other. The apparatus has a constitution in which a reducing liquid supplied through the third pipeline is mixed with a liquid mixture of a silver ion solution and an ammonia solution, the liquid mixture being supplied through the fourth pipeline.

Description

The manufacturing approach of fine silver particle, fine silver particle and the manufacturing installation of fine silver particle
[technical field]
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]
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.
In the past, as the manufacturing approach of the employed fine silver particle of e-machine material, the amine complex of known reduction silver salt made the fine silver particle deposition, 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 during the adjustment reduction.In addition, put down in writing in the patent documentation 3 through 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 manufacturing approaches, 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 small fine silver particle below 0.2～2.5 μ m or the 1 μ m.
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 through the stream that flows through at the silver-colored amine complex aqueous solution.But this manufacturing approach 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 and opens flat 8-176620 communique [patent documentation 3] spy and open 2001-107101 communique [patent documentation 4] spy and open 2005-48236 communique [patent documentation 5] spy and open the 2005-48237 communique
[summary of the invention]
[technical problem that invention will solve]
The present invention provides manufacturing approach, manufacturing installation and the fine silver particle of the fine silver particle of the problems referred to above in the solution manufacturing approach in the past, provides 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]
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.
The manufacturing approach 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; Through the karyomorphism at the nuclear that becomes aforementioned fine silver particle become material in the presence of the reduction silver ion, aforementioned fine silver particle is separated out.
The 1st mode of the manufacturing approach of fine silver particle of the present invention is through 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 manufacturing approach of fine silver particle, can be through the halide concentration of adjustment with respect to silver concentration, the particle diameter of the aforementioned fine silver particle that control 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 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, through 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%.
The 2nd mode of the manufacturing approach 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 colloidal become material to generate thus, aforementioned fine silver particle is separated out as aforementioned karyomorphism.In the 2nd the mode of the manufacturing approach of fine silver particle of the present invention, can be through the addition of adjustment aforementioned auxiliary reducing agent, the particle diameter of the aforementioned fine silver particle that control is separated out.Can secondary reducing agent 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.
The 3rd mode of the manufacturing approach of fine silver particle of the present invention is in aforementioned silver ion solution, to add Nano silver grain to become material as aforementioned karyomorphism, under this Nano silver grain, reduces aforementioned silver ion, and aforementioned fine silver particle is separated out.In the 3rd the mode of the manufacturing approach of fine silver particle,, can control the particle diameter of the aforementioned fine silver particle of separating out through 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 Nano silver grain below the 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.
The 4th mode of the manufacturing approach of fine silver particle of the present invention is in aforementioned silver ion solution, to 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.In the 4th the mode of the manufacturing approach of fine silver particle, can be through the time of adjustment from 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.
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: 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.In the manufacturing installation of fine silver particle of the present invention; The peristome that aforementioned the 3rd pipeline and aforementioned the 4th pipeline can be set to the end of its pipeline leaves ground mutually relatively 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]
Fine silver particle of the present invention is for through 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.
The manufacturing approach 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 through reduction silver ion in the presence of halide ion, can be stablized and makes this fine silver particle efficiently.The manufacturing approach 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.
In addition, the manufacturing approach of the fine silver particle of the mode according to the of the present invention the 1st is through the halide ion concentration of adjustment with respect to silver concentration, the particle diameter of the fine silver particle that control is separated out.Therefore; Through adjusting above-mentioned halogen concentration; For example, can stably obtain to be fit to the fine silver particle of particle diameter of purposes such as fine silver particle of fine silver particle or average grain diameter 0.15～0.08 μ m of fine silver particle, average grain diameter 0.5～0.15 μ m of average grain diameter 1.5～0.5 μ m efficiently.
And then the manufacturing approach 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%.
In addition; The manufacturing approach of the fine silver particle of the of the present invention the 1st mode; Reduction silver ion in the presence of halide ion; Therefore can add source of halide ions (compound) with reducing solution, need not in pipeline, to inject the so special device of reducing solution and constitute, therefore can easily implement with halide ion.
The manufacturing approach 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, in silver ion solution, in the presence of a spot of secondary reducing agent, adds 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 colloidal, and it becomes karyomorphism and becomes material and form nuclear.Small fine silver particle with colloidal 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.
In addition; The manufacturing approach of the fine silver particle of mode according to the of the present invention the 2nd; Through adjusting the addition of secondary reducing agent; The particle diameter of the fine silver particle of separating out can be controlled, for example, 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 can be stablized efficiently.
And then the manufacturing approach 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%.
In addition; The manufacturing approach of the fine silver particle of the of the present invention the 2nd mode can be united and used main reducing agent and secondary reducing agent, in the presence of secondary reducing agent, adds and becomes owner of reducing agent; Need not in pipeline, to inject this special device of reducing solution and constitute, therefore can easily implement.
The manufacturing approach 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, under this Nano silver grain, reduces the silver ion method, can stablize and makes small fine silver particle efficiently.In the manufacturing approach of the fine silver particle of the mode the of the present invention the 3rd, in solution, have a large amount of small Nano silver grains during the reduction of silver ion, 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.
In addition; The manufacturing approach of the fine silver particle of mode according to the of the present invention the 3rd; Through 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 purposes such as fine silver particle of fine silver particle or average grain diameter 0.1～0.02 μ m of fine silver particle, average grain diameter 0.5～0.1 μ m of average grain diameter 1.5～0.5 μ m.
And then the manufacturing approach 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 obtain the fine silver particle below the average grain diameter 1.5 μ m with the yield more than 99%.
In addition, the manufacturing approach 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 is restriction not, need not in pipeline, to inject this special device of reducing solution and constitutes, and can easily implement.
In the manufacturing approach 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 like fruit stone is many, and correspondingly count and increase in the aggegation center, and then the size of fine silver particle diminishes.Therefore, if become behind a large amount of ammonia that exist of silver hydroxide and silver oxide of nuclear 20 seconds in interpolation, then can stablize and obtain small fine silver particle efficiently with interior interpolation reducing agent.Particularly, for example, can obtain the small silver particles below the average grain diameter 2.5 μ m with the yield more than 99%.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.
In addition, the manufacturing approach of the fine silver particle of mode according to the of the present invention the 4th, adjustment can be made the fine silver particle of average grain diameter 0.2 μ m～2.5 μ m by adding behind the ammonia to the elapsed time of adding reducing agent.
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 manufacturing approach 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]
[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 relation of kind and the Ag particle diameter of expression halogen.[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 and fine silver particle behind the ammonia 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]
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]
Below with embodiment the present invention is described particularly.(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.
In silver ion solution, add reducing agent reduction silver ion and make in the method that fine silver particle separates out, the silver ion that under halide ion, reduces can be made fine silver particle of the present invention.In addition, in this manufacturing approach,, can control the particle diameter of the fine silver particle of separating out through the halide ion concentration of adjustment with respect to silver concentration.
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 through adding reducing agent silver.
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 separated out the amount of fine silver particle by abundant reduction.
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.What should explain is, has the tendency of enhancing according to the effect of the order microminiaturization of iodine, bromine, chlorine.
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.
If there is not halide ion, when then forming silver that the reduction of silver ion produces bunch nuclear, the essential significant amount of 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.
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 fine silver particle below the 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.
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.
In the manufacturing approach of the fine silver particle of the 1st embodiment,, can control the particle diameter of the fine silver particle of separating out through the halogen concentration of adjustment 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.
(i) through 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) through 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) through 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.
The manufacturing approach 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 of the soup of the manufacturing approach of the fine silver particle through the 1st embodiment modulation is excellent, modulate back 9 hours with the change of size of interior synthetic fine silver particle in-10%～10%.
The manufacturing approach of the fine silver particle of the 1st embodiment; Owing to there is halide ion during the reduction of silver ion, though the fine silver particle of therefore 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.
The manufacturing approach of the fine silver particle of (the 2nd embodiment) 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.Through adjusting the addition of secondary reducing agent, the particle diameter of the fine silver particle that control is separated out.
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 through interpolation reducing agent silver and separate out.
In the manufacturing approach 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.
Use main reducing agent and this secondary reducing agent stronger through 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 small fine silver particle below the average grain diameter 0.5 μ m efficiently.
What should explain is, if there is not secondary reducing agent, the reduction of the silver ion that then causes through 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.
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 colloidal 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, through 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.
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%.
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.
In the manufacturing approach of the fine silver particle of the 2nd embodiment,, can control the particle diameter of the fine silver particle of separating out through adjusting the ratio of secondary reducing agent silver.For example, when in adding the liquor argenti nitratis ophthalmicus of ammoniacal liquor, adding the hydroquinone solution reduction silver ion that contains hydrazine fine silver particle being separated out, adjust hydrazine silver as follows than (N 2H 4/ Ag) can obtain the fine silver particle of average grain diameter 1.5～0.05 μ m.
(i) through 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) through 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) through 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.
The manufacturing approach of the fine silver particle of (the 3rd embodiment) 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 through adding Nano silver grain, small fine silver particle is separated out.Through the addition of adjustment, can control the particle diameter of the fine silver particle of separating out with respect to the Nano silver grain of silver concentration.
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 through 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.
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.
Nano silver grain can use in the presence of natrium citricum, in liquor argenti nitratis ophthalmicus, adds ferrous sulfate reduction silver ion and Nano silver grain below the average grain diameter 20nm that generates.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 through this reaction silver, particle diameter can obtain to contain the silver colloidal solution of the big or small silver-colored ultramicron (Nano silver grain) of nanometer.With this silver colloidal solution Separation of Solid and Liquid, the solid separated composition is washed with natrium citricum, can obtain to be dispersed with the silver colloidal solution of Nano silver grain.
Through 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 small fine silver particle below the average grain diameter 1.5 μ m efficiently.What should explain is, if there is not 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.
For example, when in the liquor argenti nitratis ophthalmicus that adds ammoniacal liquor, adding hydroquinone solution reduction silver ion, 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 obtain the fine silver particle below the average grain diameter 1.5 μ m with the yield more than 99%.
In addition, in the manufacturing approach of the fine silver particle of the 3rd embodiment,, can control the particle diameter of the fine silver particle of separating out through the addition of adjustment 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 through 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 of the number of silver ion (below be called Nano silver grain silver ion ratio).
(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.
The manufacturing approach of the fine silver particle of (the 4th embodiment) the 4th embodiment has in silver ion solution adds ammonia and reducing agent and reduces the operation that silver ion separates out small fine silver particle; Through after adding ammonia 20 seconds with interior interpolation reducing agent, small fine silver particle is separated out.
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, through 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.
The manufacturing approach of the fine silver particle of the 4th embodiment is in silver ion solution, to add behind the ammonia 20 seconds with interior interpolation reducing agent.Through 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 silver hydroxide or the silver oxide of amine complex.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 the for example small fine silver particle below the 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.
In the manufacturing approach of the fine silver particle of the 4th embodiment, in silver ion solution, add behind the ammonia 20 seconds, therefore be not employed in and add ammonia in the silver ion solution in advance and form silver-colored amine complex, perhaps in silver ion solution, add earlier reducing agent with interior interpolation reducing agent.
In the manufacturing approach of the fine silver particle of the 4th embodiment, after adding ammonia 20 seconds with interior scope in, adjustment can be controlled the particle diameter of the fine silver particle of separating out thus by adding behind the ammonia to the elapsed time of adding reducing agent.Particularly, can adjust the elapsed time as follows and control the particle diameter of fine silver particle.
(i) through 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 through 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 through 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 through the above-mentioned elapsed time is adjusted into.
The manufacturing installation of the fine silver particle of this 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 this 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 and relatively each other a little.
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.
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 by hybrid position A to long (flow path length) L of the pipeline of hybrid position B (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 pipeline of the 4th pipeline 16 long) decide, set pipeline length (flow path length) L to add behind the ammonia 20 seconds with the mode of interior interpolation reducing solution.
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.
During said apparatus constituted, the 4th pipeline 16 and the 3rd pipeline 15 that hybrid position B is set were relative so that the peristome of the end of its pipeline leaves mutually a little.The peristome of the end of pipeline is oppositely arranged with leaving mutually; The silver ion solution of the interpolation ammonia that flows through the 4th pipeline 16 thus, with mix in the outside of pipeline through the 3rd pipeline 15 mobile reducing solutions, 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.
What should explain is; Through 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, and a part of opening of the portion of reporting to the leadship after accomplishing a task, mixed liquor are made up of what peristome promptly sprayed 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]
Followingly the present invention is described particularly according to embodiment.What should explain is that the mensuration of particle diameter is tried to achieve with the calculation of number benchmark through laser light scattering/diffraction approach.
(embodiment 1) has added the hydroquinone solution of ammonium iodide solution in the liquor argenti nitratis ophthalmicus that adds ammoniacal liquor, 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.What should explain is that in the table 2, Sample A 1～A11 is a sample of the present invention.With do not add ammonium iodide solution as duplicate 1a, will be than the excessive example of iodine addition preferred range as duplicate 1b.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.
[table 1]
Figure G2008800069565D00201
[table 2]
Figure G2008800069565D00202
, do not add in the duplicate of ammonium iodide with shown in Figure 1 like table 2, 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.
In addition, like table 2 with 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 of the soup that the present invention uses is excellent, modulates the back 9 hours particle diameters with interior synthetic fine silver particle also in-10%～10% scope.
Hydroquinone solution (the halid molal quantity: 2.82 * 10 that adds ammonium halide solution is in advance added in (embodiment 2) in the liquor argenti nitratis ophthalmicus that adds ammoniacal liquor -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.This result is shown in table 3 and Fig. 7～Figure 10.What should explain is that in the table 3, sample B 1～sample B 3 is sample of the present invention.With not adding ammonium halide solution person as duplicate 2.Halide salt aqueous solution is the 0.1M aqueous solution, and silver-colored solution is identical with table 1 with reducing solution.Like 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.
[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
(embodiment 3) replace the ammonium halide solution of embodiment 2, use the halide salt aqueous solution shown in the table 4, in addition with embodiment 2 identical condition reduction silver ions fine silver particle is separated out, measure the average grain diameter of the fine silver particle of separating out.The assay method of average grain diameter is identical with embodiment 1.This result is shown in table 4.What should explain is that in the table 4, sample C1～sample C3 is a sample of the present invention.With do not add the halide salt aqueous solution as duplicate 3.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.
[table 4]
Figure G2008800069565D00221
(comparative example 1) uses the liquor argenti nitratis ophthalmicus of the adding ammoniacal liquor shown in table 5 (duplicate 4) and the table 6 (duplicate 5), in this solution, adds hydroquinone solution, and 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.This result is shown in table 7.In reducing solution, do not add in advance under the situation of halide ion, can obtain average grain diameter through the dilution silver concentration is the fine silver particle below the 0.50 μ m, but yield is lower than 99% owing to be difficult to reclaim.
[table 5]
Figure G2008800069565D00231
[table 6]
[table 7]
Duplicate 4 Duplicate 5
Ag particle diameter (μ m) 0.35 0.47
Yield (%) 96.7 97.9
The liquor argenti nitratis ophthalmicus of adding ammoniacal liquor as shown in table 8 is used in (embodiment 4); 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 through laser-scattering/diffraction approach.The result who obtains is shown in table 9.What should explain is, in the table 9, sample D1～D11 is a sample of the present invention, with do not add secondary reducing agent as duplicate.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.
[table 8]
Figure G2008800069565D00241
[table 9]
Figure G2008800069565D00251
(embodiment 5～embodiment 6) uses sodium borohydride solution (embodiment 5), perhaps uses boron hydride dimethyl amine solution (embodiment 6) as secondary reducing agent C as secondary reducing agent B, and other are identical with embodiment 4, makes fine silver particle.This result is 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.
[table 10]
NaBH4 measures (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
[table 11]
BH 3HN (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
Like 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.
In addition, 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 of the soup of modulation is excellent 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.
(comparative example 2) uses the liquor argenti nitratis ophthalmicus of the adding ammoniacal liquor shown in table 12 (duplicate 11) and table 13 (duplicate 12), in this solution, adds hydroquinone solution, and 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.This result is shown in table 14.In the situation of not adding secondary reducing agent, can obtain average grain diameter through the dilution silver concentration is the fine silver particle below the 0.50 μ m, but yield is lower than 99% owing to be difficult to reclaim.
[table 12]
Figure G2008800069565D00261
[table 13]
Figure G2008800069565D00262
[table 14]
Duplicate 11 Duplicate 12
Ag particle diameter (μ m) 0.35 0.47
Yield (%) 96.7 97.9
The liquor argenti nitratis ophthalmicus of adding ammoniacal liquor as shown in Tble 15 is used in (embodiment 7), in this solution, adds Nano silver grain in advance, and then adds hydroquinone solution, and 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 through SEM.The result who obtains is shown in table 16～table 17 and Figure 18～Figure 23.What should explain is, sample G1～G5, H1～H3, J1～J3, K are sample of the present invention, with do not add Nano silver grain as duplicate.
Like 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.What should explain is that among sample G～J, the Nano silver grain that uses citric acid method to prepare among the sample K, uses the Nano silver grain of the 50nm of method for making not quite clear (non-opening shown).
[table 15]
[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 - 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
[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 16.4 931 * 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
(comparative example 3) uses the liquor argenti nitratis ophthalmicus of the adding ammoniacal liquor shown in table 18 (duplicate 17) and table 19 (duplicate 18), in this solution, adds hydroquinone solution, and 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.This result is shown in table 20.Under the situation of not adding Nano silver grain, through the dilution silver concentration, also can obtain average grain diameter is the fine silver particle below the 0.50 μ m, but yield is lower than 99% owing to be difficult to reclaim.
[table 18]
Figure G2008800069565D00291
[table 19]
[table 20]
Duplicate 17 Duplicate 18
Ag particle diameter (μ m) 0.35 0.47
Yield (%) 96.7 97.9
(embodiment 8 and comparative example 4) uses 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 in liquor argenti nitratis ophthalmicus, to add behind the ammoniacal liquor 20 seconds on one side.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.
The result of sample L1～L7 of the present invention is shown in table 22.The result of duplicate M1～M5 is shown in table 23.The relation of in liquor argenti nitratis ophthalmicus, adding 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.
With shown in Figure 25, (i) the above-mentioned elapsed time is in 0.3 second～0.5 second the time like table 22, 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.
[table 21]
[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
[table 23]
Figure G2008800069565D00321
[industrial applicability]
According to the manufacturing approach 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 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 wiring material that becomes electronic device or electrode material, and the manufacturing approach of fine silver particle of the present invention and manufacturing installation are applicable to the manufacturing process of this silver particles in addition.

Claims (6)

1. fine silver particle is characterized in that, in fine silver particle with respect to silver, with 5.0 * 10 -8～1.8 * 10 -6Mol ratio contain halogen, and average grain diameter is 1.5～0.5 μ m.
2. the manufacturing approach 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,
Through the aforementioned silver ion of reduction in the presence of halide ion, make silver halide become material and generate as the karyomorphism of the nuclear that will become aforementioned fine silver particle, wherein the amount of halide ion does, with respect to silver, the mol ratio of halide ion is 5.0 * 10 -8～1.5 * 10 -3,
Through become at aforementioned karyomorphism material in the presence of the reduction aforementioned silver ion, aforementioned fine silver particle is separated out.
3. the manufacturing approach of fine silver particle as claimed in claim 2 wherein, through the halide concentration of adjustment with respect to silver concentration, is controlled the particle diameter of the aforementioned fine silver particle of separating out.
4. the manufacturing approach of fine silver particle as claimed in claim 3.Wherein, use the liquor argenti nitratis ophthalmicus that adds ammoniacal liquor, use hydroquinone solution,, use NH as compound with aforementioned halide ion as aforementioned reducing agent as aforementioned silver ion solution 4Cl, NH 4Br, NH 4I, KCl, KBr, KI, NaCl, NaBr or NaI.
5. the manufacturing approach of fine silver particle as claimed in claim 2 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 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) the mol ratio I/Ag of aforementioned iodine with respect to silver 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) the mol ratio I/Ag of aforementioned iodine with respect to silver 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.
6. the manufacturing approach of fine silver particle as claimed in claim 2; 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, through 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%.
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