CN103702786B - Silver microparticle and the conductive paste containing this silver-colored microparticle, conductive film and electronic device - Google Patents
Silver microparticle and the conductive paste containing this silver-colored microparticle, conductive film and electronic device Download PDFInfo
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- CN103702786B CN103702786B CN201280036601.7A CN201280036601A CN103702786B CN 103702786 B CN103702786 B CN 103702786B CN 201280036601 A CN201280036601 A CN 201280036601A CN 103702786 B CN103702786 B CN 103702786B
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- silver
- colored microparticle
- microparticle
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- crystallite diameter
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
- B22F1/054—Nanosized particles
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
Abstract
The invention provides that be suitable as can the silver-colored microparticle of raw material of conductive paste etc. of low-firing and conductive paste, conductive film and the electronic device containing this silver-colored microparticle.The feature of silver-colored microparticle of the present invention is, ratio [the crystallite diameter D of the Miller indices (111) obtained by X-ray diffraction and the crystallite diameter of (200)
x(111)/crystallite diameter D
x(200) be] more than 1.40.
Description
Technical field
The present invention relates to be suitable as can the raw material of conductive paste of low-firing use, average grain diameter for more than 100nm or average grain diameter be less than 100nm silver-colored microparticle and containing the conductive paste of this silver-colored microparticle, conductive film and electronic device.
Background technology
The electrode of electronic device or the formation of circuit pattern, to print electrode on substrate containing the conductive paste of metallic particles or after circuit pattern by using, carry out heating the metal particles sinter firing and make to contain in conductive paste and carry out, can be categorized as according to heating firing temperature and fire type cream and polymer-type cream.In recent years, this heating firing temperature is in the trend of low temperature.
The type cream of firing generally uses in ceramic substrate, and using metallic particles and frit, solvent etc. as main component, its heating firing temperature is more than about 500 DEG C.On the other hand, polymer-type cream uses in film distributing board or conductive adhesive etc., be dispersed in by metallic particles the cream obtained in resin, curing agent, organic solvent, dispersant etc. to be formed, serigraphy etc. is utilized this conductive paste to be formed on substrate the conductive pattern of regulation, until the temperature of about 250 DEG C is carried out heating and fired and use.
As above-mentioned metallic particles, copper powder and silver powder can be used, especially, be formed in the serigraphy conductive paste used at the circuit of film distributing board, use silver as conductive particle.Although silver has the shortcoming that migration easily occurs, with have same degree resistivity copper compared be difficult to be oxidized, therefore easily process, be widely utilized.
In recent years, the heating firing temperature of conductive paste is in the trend of low temperature.Such as, as the installation base plate of electronic device, generally can be heated to about 300 DEG C, excellent heat resistance, therefore, uses the flexible base board of polyimides, but it is expensive, therefore, recently, have studied the PET(PETG that use is more cheap) substrate or PEN(PEN) substrate instead material.But pet substrate or PEN substrate are compared with the flexible base board of polyimides, and heat resistance is low, especially, the PET film substrate used in film distributing board needs below 150 DEG C, carry out heating and fires.
In addition, fire if heating can be carried out in the temperature lower than 200 DEG C, so also can form electrode or circuit pattern on the substrate of Merlon or paper etc., the purposes expansion of various electrode materials etc. can be expected.
As the metallic particles that can carry out the raw material of the conductive paste of such low-firing, the silver-colored microparticle of nanometer scale is expected.As its reason, be because: when the size of metallic particles reaches nanometer scale, surface-active uprises, and compared with metal derby, fusing point reduces far away, therefore, it is possible to make it sinter in low temperature.
In addition, the silver-colored microparticle of nanometer scale, also as make use of can in low-temperature sintering and can maintain when once sintered heat resistance such, the lead-free solder of character that solder does not in the past have replaces material to be expected.
Up to the present, as the wiring material of electronic device or the silver-colored microparticle of electrode material, and can the silver-colored microparticle of low-firing, propose the silver-colored microparticle of submicron-scale to micron-scale, there will be a known: the spherical silver powder (patent document 1) that crystallite diameter is limited relative to the ratio of BET specific surface area; To the silver-colored microparticle (patent document 2) that average grain diameter, crystallite diameter and average grain diameter limit relative to the ratio of crystallite diameter; To the silver powder (patent document 3) that tap density, laser diffractometry average grain diameter and specific area limit; The average grain diameter of primary particle is 0.05 ~ 1.0 μm and crystallite diameter is the manufacture method (patent document 4) of the silver-colored microparticle of 20 ~ 150nm; Average grain diameter is more than 0.1 μm and is less than 1 μm and the precipitous and dispersed high spherical silver powder (patent document 5) of size distribution; Primary particle diameter is 0.07 ~ 4.5 μm and crystallite diameter is the high crystallization silver powder (patent document 6) of more than 20nm; Containing the temperature range of silver-colored reaction process has been carried out restriction, primary particle diameter is at the composition (patent document 7) etc. of the small Argent grain of 1 ~ 100nm scope.
Prior art document
Patent document
Patent document 1: Japanese Unexamined Patent Publication 2005-330529 publication
Patent document 2: Japanese Unexamined Patent Publication 2006-183072 publication
Patent document 3: Japanese Unexamined Patent Publication 2007-131950 publication
Patent document 4: Japanese Unexamined Patent Publication 2008-31526 publication
Patent document 5: Japanese Unexamined Patent Publication 2010-70793 publication
Patent document 6: Japanese Unexamined Patent Publication 2007-16258 publication
Patent document 7: Japanese Unexamined Patent Publication 2009-120949 publication
Summary of the invention
The technical problem that invention will solve
Silver-colored microparticle disclosed in above-mentioned patent document 1 to patent document 6, each define average grain diameter and crystallite diameter, BET specific surface area value etc., but all do not consider ratio [the crystallite diameter D of the crystallite diameter of Miller indices (111) and (200) obtained by X-ray diffraction
x(111)/crystallite diameter D
x(200)], as shown in aftermentioned comparative example, at above-mentioned crystallite diameter D
x(111)/crystallite diameter D
x(200), when] being less than 1.40, the silver-colored microparticle obtaining having good low-temperature sintering is difficult to.In addition, at crystallite diameter D
x(111), when more than 20nm, the crystallite diameter of silver-colored microparticle is large, therefore, the reactive step-down of silver-colored microparticle inside, unfavorable to low-temperature sintering.
Therefore, technical problem of the present invention be to provide be suitable as can low-firing conductive paste raw material use silver-colored microparticle.In addition, the object of the invention is to obtain: the average grain diameter of the silver-colored microparticle obtained is wide region, be particularly preferably more than 30nm and be less than 100nm and more than 100nm and be less than the silver-colored microparticle of 1 μm.
For the means of technical solution problem
Above-mentioned technical problem can be solved by the present invention as described below.
That is, the present invention is a kind of silver-colored microparticle, it is characterized in that, ratio [the crystallite diameter D of the Miller indices (111) obtained by X-ray diffraction and the crystallite diameter of (200)
x(111)/crystallite diameter D
x(200)] be more than 1.40 (the present invention 1).
In addition, the present invention is the silver-colored microparticle as described in the present invention 1, it is characterized in that, average grain diameter (D
sEM) to be less than 1 μm (the present invention 2) for more than 100nm.
In addition, the present invention is the silver-colored microparticle as described in the present invention 1 or 2, it is characterized in that, the crystallite diameter D of Miller indices (111)
x(111) be below 20nm (the present invention 3).
In addition, the present invention is the silver-colored microparticle according to any one of the present invention 1 ~ 3, it is characterized in that, the crystallite diameter D of Miller indices (200)
x(200) be below 14nm (the present invention 4).
In addition, the present invention is the silver-colored microparticle according to any one of the present invention 1 ~ 4, it is characterized in that, the particle surface of silver-colored microparticle is by one kind or two or more coated (the present invention 5) that are selected from the high score subclass dispersant of number-average molecular weight more than 1000.
In addition, the present invention is the silver-colored microparticle as described in the present invention 1, it is characterized in that, average grain diameter (D
sEM) for more than 30nm and be less than 100nm(the present invention 6).
In addition, the present invention is the silver-colored microparticle as described in the present invention 1 or 6, it is characterized in that, the crystallite diameter D of Miller indices (111)
x(111) be below 25nm (the present invention 7).
In addition, the present invention is the silver-colored microparticle according to any one of the present invention 1,6 and 7, it is characterized in that, the crystallite diameter D of Miller indices (200)
x(200) be below 15nm (the present invention 8).
In addition, the present invention is the silver-colored microparticle according to any one of the present invention 1 and 6 ~ 8, it is characterized in that, the particle surface of silver-colored microparticle is by the macromolecular compound of molecular weight more than 10000 coated (the present invention 9).
In addition, the present invention is a kind of conductive paste, it is characterized in that, containing the silver-colored microparticle (the present invention 10) according to any one of the present invention 1 ~ 9.
In addition, the present invention is a kind of conductive film, it is characterized in that, uses the conductive paste described in the present invention 10 to form (the present invention 11).
In addition, the present invention is a kind of electronic device, it is characterized in that, has the conductive film (the present invention 11) described in the present invention 11.
Invention effect
Silver-colored microparticle of the present invention, ratio [the crystallite diameter D of the crystallite diameter of the Miller indices obtained by X-ray diffraction (111) and (200)
x(111)/crystallite diameter D
x(200) be] more than 1.40, therefore, being suitable as can the raw material of conductive paste etc. of low-firing.
Detailed description of the invention
Technical scheme of the present invention is described as follows in more detail.
First, silver-colored microparticle of the present invention is described.
The feature of silver-colored microparticle of the present invention is, ratio [the crystallite diameter D of the Miller indices (111) obtained by X-ray diffraction and the crystallite diameter of (200)
x(111)/crystallite diameter D
x(200) be] more than 1.40.
The average grain diameter of silver-colored microparticle of the present invention, can determine according to condition required in purposes, from the view point of manufacture method, can be categorized as average grain diameter (D in wide region
sEM) be the situation of more than 100nm (first method) and average grain diameter (D
sEM) be less than 100nm(second method) and situation.
First, above-mentioned first method is described.In first method, the average grain diameter (D of silver-colored microparticle of the present invention
sEM) be more than 100nm, be preferably more than 100nm and be less than 1 μm, being more preferably 100 ~ 500nm.By average grain diameter (D
sEM) in above-mentioned scope, easily the becoming more meticulous of reply distribution and electrode.At average grain diameter (D
sEM) when being less than 100nm, even if also easily sinter at normal temperature, in addition, the dispersiveness in conductive paste and dispersion stabilization are in the trend of reduction, therefore, have the situation of the such scheme needing to record in second method.At average grain diameter (D
sEM) more than 1 μm when, agglutinating property under low temperature reduces, therefore not preferred.In addition, because particle size is excessive, so becoming more meticulous of the electronic device using this silver-colored microparticle to obtain becomes difficulty.
Ratio [the crystallite diameter D of the Miller indices (111) obtained by X-ray diffraction of the silver-colored microparticle of the 1st aspect of the present invention and the crystallite diameter of (200)
x(111)/crystallite diameter D
x(200) be] more than 1.40, be preferably more than 1.44, be more preferably more than 1.48.By making crystallite diameter D
x(111) with crystallite diameter D
x(200) ratio is more than 1.40, can obtain the silver-colored microparticle of low-temperature sintering excellence.
The crystallite diameter D of the Miller indices (111) obtained by X-ray diffraction of the silver-colored microparticle of the 1st aspect of the present invention
x(111) be preferably below 20nm, be more preferably 10 ~ 19nm, be more preferably 10 ~ 18nm further.At crystallite diameter D
x(111), when more than 20nm, the reactivity in silver-colored microparticle reduces, and can damage low-temperature sintering, therefore not preferred.In addition, at crystallite diameter D
x(111) when being less than 10nm, silver-colored microparticle becomes unstable, even if also partly start to sinter at normal temperature, welding, therefore not preferred.
The crystallite diameter D of the Miller indices (200) obtained by X-ray diffraction of the silver-colored microparticle of the 1st aspect of the present invention
x(200) be preferably below 14nm, be more preferably below 13nm, be more preferably below 12nm further.In order to make [crystallite diameter D
x(111)/crystallite diameter D
x(200) be] more than 1.40, crystallite diameter D
x(200) more little more preferred.
The low-temperature sintering of the silver-colored microparticle of the 1st aspect of the present invention, the rate of change [(crystallite diameter of the silver-colored microparticle before the crystallite diameter/heating of the silver-colored microparticle of 150 DEG C of heating after 30 minutes) × 100] by heating the crystallite diameter caused described later is utilized to evaluate, the rate of change of the crystallite diameter caused by the heating of 150 DEG C is preferably more than 120%, is more preferably more than 125%.When the rate of change of crystallite diameter is less than 120%, be difficult to low-temperature sintering excellence.In the present invention, when heating 30 minutes for 210 DEG C, the rate of change of crystallite diameter is preferably more than 150%, is more preferably more than 170%.
The BET specific surface area value of the silver-colored microparticle of the 1st aspect of the present invention is preferably 5m
2/ below g.In BET specific surface area value more than 5m
2when/g, the viscosity of the conductive paste using this silver-colored microparticle to obtain uprises, therefore not preferred.
Average grain diameter (the D of the silver-colored microparticle of the 2nd aspect of the present invention
sEM) be less than 100nm, be preferably more than 30nm and be less than 100nm, be more preferably more than 35nm and be less than 100nm.By average grain diameter (D
sEM) in above-mentioned scope, the becoming more meticulous of electronic device using this silver-colored microparticle to obtain becomes easy.At average grain diameter (D
sEM) when being less than 30nm, the surface-active that silver-colored microparticle has uprises, and in order to stably maintain its fine particle diameter, needs to make the attachments such as a large amount of organic matters, therefore not preferred.
Ratio [the crystallite diameter D of the Miller indices (111) obtained by X-ray diffraction of the silver-colored microparticle of the 2nd aspect of the present invention and the crystallite diameter of (200)
x(111)/crystallite diameter D
x(200) be] more than 1.40, be preferably more than 1.44, be more preferably more than 1.48.By making crystallite diameter D
x(111) with crystallite diameter D
x(200) ratio is more than 1.40, can obtain the silver-colored microparticle of low-temperature sintering excellence.
The crystallite diameter D of the Miller indices (111) obtained by X-ray diffraction of the silver-colored microparticle of the 2nd aspect of the present invention
x(111) be preferably below 25nm, be more preferably 23 ~ 10nm, be more preferably 20 ~ 10nm further.At crystallite diameter D
x(111), when more than 25nm, the reactivity in silver-colored microparticle reduces, and can damage low-temperature sintering, therefore not preferred.In addition, at crystallite diameter D
x(111) when being less than 10nm, silver-colored microparticle becomes unstable, even if also partly start to sinter at normal temperature, welding, therefore not preferred.
The crystallite diameter D of the Miller indices (200) obtained by X-ray diffraction of the silver-colored microparticle of the 2nd aspect of the present invention
x(200) be preferably below 15nm, be more preferably below 14nm, be more preferably below 13nm further.In order to make [crystallite diameter D
x(111)/crystallite diameter D
x(200) be] more than 1.40, crystallite diameter D
x(200) more little more preferred.
The low-temperature sintering of the silver-colored microparticle of the 2nd aspect of the present invention, the rate of change [(crystallite diameter of the silver-colored microparticle before the crystallite diameter/heating of the silver-colored microparticle of 150 DEG C of heating after 30 minutes) × 100] by heating the crystallite diameter caused described later is utilized to evaluate, the rate of change of the crystallite diameter caused by the heating of 150 DEG C is preferably more than 150%, is more preferably more than 160%.When the rate of change of crystallite diameter is less than 150%, be difficult to low-temperature sintering excellence.In the present invention, when heating 30 minutes for 210 DEG C, the rate of change of crystallite diameter is preferably more than 180%, is more preferably more than 200%.
The BET specific surface area value of the silver-colored microparticle of the 2nd aspect of the present invention is preferably 10m
2/ below g, is more preferably 8m
2/ below g.In BET specific surface area value more than 10m
2when/g, the viscosity of the conductive paste using this silver-colored microparticle to obtain uprises, therefore not preferred.
The grain shape of the silver-colored microparticle of the 1st aspect of the present invention and second method, is preferably spherical or granular.
Silver-colored microparticle of the present invention is preferably one kind or two or more coated by what be selected from high score subclass dispersant.In the silver-colored microparticle of the 1st aspect of the present invention and the silver-colored microparticle of second method, high score subclass dispersant preferably uses according to number-average molecular weight difference.
The silver-colored microparticle of the 1st aspect of the present invention, the particle surface of preferred silver-colored microparticle is one kind or two or more coated by what be selected from the high score subclass dispersant of number-average molecular weight more than 1000.The number-average molecular weight of dispersant is preferably more than 1000, is more preferably 1000 ~ 150000, is more preferably 5000 ~ 100000 further.The dispersant being less than 1000 by number-average molecular weight carries out surface-treated silver microparticle powder, and insufficient by the effect of dispersant process, in pulverization process thereafter, silver-colored microparticle has the trend of aggegation.On the other hand, when number-average molecular weight is more than 150000, the viscosity of dispersant uprises, and is difficult to process uniformly silver-colored microparticle surfaces.
The silver-colored microparticle of the 2nd aspect of the present invention, the particle surface of preferred silver-colored microparticle is coated by the macromolecular compound (high score subclass dispersant) of molecular weight more than 10000.When molecular weight is less than 10000, can produce aggegation block in the pulverization process of carrying out thereafter, the silver-colored microparticle obtained is difficult to disperse in conductive paste, therefore not preferred.In addition, the upper limit of the molecular weight of high score subclass dispersant is about 100000, and when molecular weight is prescribed a time limit higher than on this, viscosity uprises, and is difficult to process uniformly silver-colored microparticle surfaces.
When using the high score subclass dispersant of above-mentioned any molecular weight, when considering macromolecular compound to the uniformity of the process of silver-colored microparticle surfaces and treatment effect, as dispersant, preferably there is (have acidic functionality and basic functionality) dispersant of acid number and amine value or will there is the dispersant of acid number and there is the dispersant of amine value and use.
Although the covering amount of dispersant is also different according to the BET surface area values of silver-colored microparticle, is preferably 0.1 ~ 3.0 % by weight relative to silver-colored microparticle powder, is more preferably 0.2 ~ 2.5 % by weight.When being less than 0.1 % by weight, the treating capacity of dispersant is insufficient, and in pulverization process thereafter, silver-colored microparticle powder has the trend of aggegation.When more than 3.0 % by weight, although the aggegation of silver-colored microparticle powder can be suppressed, increase with the organic components that electric conductivity is irrelevant, therefore not preferred.
As above-mentioned high score subclass dispersant, generally commercially available as pigment dispersing agent material can be used, specifically, can enumerate: ANTI-TERRA-U, ANTI-TERRA-205, DISPERBYK-101, DISPERBYK-102, DISPERBYK-106, DISPERBY K-108, DISPERBYK-109, DISPERBYK-110, DISPERBYK-111, DI SPERBYK-112, DISPERBYK-116, DISPERBYK-130, DISPERBYK-140, DISPERBYK-142, DISPERBYK-145, DISPERBYK-161, DISP ERBYK-162, DISPERBYK-163, DISPERBYK-164, DISPERBYK-166, DISPERBYK-167, DISPERBYK-168, DISPERBYK-170, DISPER BYK-171, DISPERBYK-174, DISPERBYK-180, DISPERBYK-182, DISPERBYK-183, DISPERBYK-184, DISPERBYK-185, DISPERBY K-2000, DISPERBYK-2001, DISPERBYK-2008, DISPERBYK-2009, DISPERBYK-2022, DISPERBYK-2025, DISPERBYK-2050, DISPER BYK-2070, DISPERBYK-2096, DISPERBYK-2150, DISPERBYK-2155, DISPERBYK-2163, DISPERBYK-2164, BYK-P104, BYK-P104S, BYK-P105, BYK-9076, BYK-9077, BYK-220S, (the Japanese Co., Ltd of Bi Ke chemistry manufactures), EFKA4008, EFKA4009, EFKA4046, EF KA4047, EFKA4010, EFKA4015, EFKA4020, EFKA4050, EFKA4055, EFKA4060, EFKA4080, EFKA4300, EFKA
4330, EFKA4400, EFKA4401, EFKA4402, EFKA4403, EFKA4406, EFKA4800, EFKA5010, EFKA5044, EFKA5244, EFKA5054, EFKA5055, EFKA5063, EFKA5064, EF KA5065, EFKA5066, EFKA5070(BASF Amada Co., Ltd. (BAS F Japan Ltd.) manufactures), SOLSPERSE3000, SOLSPERSE13240, S OLSPERSE13940, SOLSPERSE16000, SOLSPERSE17000, SO LSPERSE18000, SOLSPERSE20000, SOLSPERSE21000, SOL SPERSE24000SC, SOLSPERSE24000GR, SOLSPERSE26000, SOLSPERSE27000, SOLSPERSE28000, SOLSPERSE31845, S OLSPERSE32000, SOLSPERSE32500, SOLSPERSE32550, SO LSPERSE34750, SOLSPERSE35100, SOLSPERSE35200, SOL SPERSE36000, SOLSPERSE36600, SOLSPERSE37500, SOLS PERSE38500, SOLSPERSE39000, SOLSPERSE41000(Japan Lu Borun Co., Ltd. (Lubrizol Corporation, Japan) manufacture), AJISPER PB821, AJISPER PB822, AJISPER PB881, AJISPER PN-411, AJISPER PA-111, (aginomoto fine chemistry Co., Ltd. (Ajinomoto Fine-Techno Co., I nc.) manufacture), DISPARLON KS-860, DISPARLON KS-873N, DIS PARLON7004, DISPARLON1831, DISPARLON1850, DISPA RLON1860, DISPARLON DA-7301, DISPARLON DA-325, DI SPARLON DA-375, DISPARLON DA-234(nanmu originally change into Co., Ltd. and manufacture), Flowlen DOPA-15B, Flowlen DOPA-17HF, Flowlen DOP A-22, Flowlen DOPA-33, Flowlen G-700, Flowlen G-820, Flo wlen G-900(Kyoeisha Chemical Co., Ltd. manufacture) etc.These pigment dispersing agents can use a kind or two or more combinationally used.
Then, the manufacture method of silver-colored microparticle of the present invention is described.
Silver-colored microparticle of the present invention, can be obtained by following any manufacture method: the manufacture method of the silver-colored microparticle that the aqueous solution added containing reducing agent makes the reduction of silver-colored microparticle separate out in the aqueous solution containing silver salt complex; Or in reducing solution, add the manufacture method of the silver-colored microparticle that silver nitrate aqueous solution makes the reduction of silver-colored microparticle separate out.In addition, as the average grain diameter (D of the 2nd aspect of the present invention
sEM) be less than the manufacture method of the silver-colored microparticle of 100nm, the alcoholic solution adding silver salt complex in reductant solution also can be adopted to make silver-colored microparticle reduce the manufacture method of silver-colored microparticle of the solvent reaction system separated out.In any case, the temperature range importantly below 30 DEG C is carried out from being reacted to dry whole operations.
When the manufacture method of the silver-colored microparticle that the aqueous solution added containing reducing agent in the aqueous solution containing silver salt complex makes the reduction of silver-colored microparticle separate out, the previously prepared aqueous solution containing silver salt complex and the aqueous solution containing reducing agent respectively.
Silver salt complex in the present invention, can by being obtained by mixing as the silver nitrate of silver material or silver acetate and ammoniacal liquor, ammonium salt or complex compound etc.As the addition of ammonia, because the ligancy of the ammonia in amine complex is 2, so, the ammonia of more than 2 moles is preferably added relative to silver 1 mole.When considering the improvement of production stability and the size distribution of silver-colored microparticle that obtains, the addition of ammonia is more preferably more than 4 moles relative to every 1 moles of silver, is more preferably more than 10 moles further.
As the reducing agent in the present invention, can use that to be selected from arabo-ascorbic acid, ascorbic acid, alkanolamine, quinhydrones, glucose, pyrogallol, hydrazine, hydrogen peroxide and formaldehyde one kind or two or more.Improve from the view point of the dispersiveness of the silver-colored microparticle making to obtain in conductive paste, preferably use organic reducing agent, be more preferably arabo-ascorbic acid or ascorbic acid.
The addition of reducing agent, preferably adds more than 1.0 moles relative to silver 1 mole, is more preferably 1.0 ~ 2.0 moles.Especially, when using ascorbic acid or arabo-ascorbic acid as reducing agent, when relative to silver 1 mole of interpolation more than 2.0 moles, the silver-colored microparticle of generation has the trend of aggegation each other, therefore not preferred.
When adding the manufacture method of the silver-colored microparticle that silver nitrate aqueous solution makes the reduction of silver-colored microparticle separate out in reducing solution, also distinguish previously prepared reducing solution and silver nitrate aqueous solution.
Silver nitrate aqueous solution in the present invention, can by being obtained by mixing silver nitrate and ion exchange water or pure water.The concentration of the silver nitrate in the aqueous solution, is preferably the scope of 0.08 ~ 2.0mol/l, is more preferably 0.1 ~ 1.8mol/l.
Reducing solution can by by ammoniacal liquor with ion exchange water or pure water with reducing agent mixes, stir and obtain.In addition, as the reducing agent used in reducing solution, above-mentioned reducing agent can be used.
The addition of reducing agent, preferably adds more than 1.0 moles relative to silver 1 mole, is more preferably 1.0 ~ 2.0 moles.Especially, when using ascorbic acid or arabo-ascorbic acid as reducing agent, when relative to silver 1 mole of interpolation more than 2.0 moles, the silver-colored microparticle of generation has the trend of aggegation each other, therefore not preferred.
When preparing the aqueous solution containing silver salt complex, the aqueous solution, reducing solution and silver nitrate aqueous solution containing reducing agent, preferably liquid temperature is remained on less than 18 DEG C, by the aqueous solution containing silver salt complex and containing the aqueous solution of reducing agent or reducing solution and silver nitrate aqueous solution mixing, stir time, also preferably adjustment makes liquid temperature be no more than 20 DEG C.When reaction temperature is more than 20 DEG C, the crystallite diameter D of silver-colored microparticle
x(111) become large and crystallite diameter D
x(111)/crystallite diameter D
x(200) ratio becomes and is less than 1.40, and low-temperature sintering suffers damage, therefore not preferred.
The aqueous solution containing reducing agent, to the interpolation in the aqueous solution containing silver salt complex or silver nitrate aqueous solution to the interpolation in reducing solution, preferably carries out in the time short as far as possible, within being more preferably 20 seconds, within being more preferably further 15 seconds.When the aqueous solution containing reducing agent to the interpolation time in the aqueous solution containing silver salt complex or silver nitrate aqueous solution elongated to the interpolation time in reducing solution time, the silver-colored microparticle generated produces aggegation each other, particle size becomes large, and size distribution is in the large trend of change.
Add the aqueous solution containing reducing agent in the aqueous solution containing silver salt complex after or add silver nitrate aqueous solution in reducing solution after, carry out lentamente stirring, mixing the silver-colored microparticle not aggegation each other making to generate, then, usual method is utilized to carry out filtering, washing.Now, carry out cleaning until the electrical conductivity of filtrate becomes 60 below μ S/cm.
The filter cake of the silver-colored microparticle obtained is made to be redispersed in hydrophilic organic solvent, after the moisture of silver-colored microparticle surfaces is replaced into hydrophilic organic solvent, utilize usual method to filter, use drying machine or vacuum drying to carry out drying temperature less than 30 DEG C the silver-colored microparticle obtained.When baking temperature is more than 30 DEG C, the crystallite diameter D of silver-colored microparticle
x(111) become large and crystallite diameter D
x(111)/crystallite diameter D
x(200) ratio becomes and is less than 1.40, and low-temperature sintering suffers damage, therefore not preferred.By the moisture of silver-colored microparticle surfaces is replaced into hydrophilic organic solvent, dried silver-colored microparticle can be prevented to be each the state of firmly aggegation, and pulverization process thereafter or surface treatment, pulverization process etc. become easy.
As hydrophilic organic solvent, alcohol and the acetone etc. such as methyl alcohol, ethanol, propyl alcohol can be used.When considering by drying, solvent to be removed, particular methanol and ethanol.
Utilize the manufacture method of above-mentioned water-based reaction system, the silver-colored microparticle of the average grain diameter of the any-mode in first method and second method can be manufactured, as the method controlling particle diameter, the concentration adjustment of the ammoniacal liquor in the concentration adjustment of the silver nitrate in silver nitrate aqueous solution, reducing solution can be enumerated.Such as by making the concentration of the silver nitrate in silver nitrate aqueous solution improve, the concentration of the ammoniacal liquor in reducing solution is reduced, the silver-colored microparticle of the average grain diameter being mainly first method can be manufactured, on the contrary, reduce by making the concentration of the silver nitrate in silver nitrate aqueous solution, the concentration of the ammoniacal liquor in reducing solution is improved, the silver-colored microparticle of the average grain diameter being mainly second method can be manufactured.
The alcoholic solution of the silver salt complex in the solvent reaction system that the alcoholic solution adding silver salt complex in reductant solution makes silver-colored microparticle reduce to separate out, can be obtained by the aliphatic amine of the carbon number 2 ~ 4 of the water-soluble or water dissolvable of the silver of mixed nitrate in alcoholic solution and more than a kind.Aliphatic amine is preferably 2.0 ~ 2.5 moles relative to silver nitrate 1 mole, is more preferably 2.0 ~ 2.3 moles.When the amount of aliphatic amine is less than 2.0 moles relative to silver nitrate 1 mole, there is the trend easily generating large particle.
As the aliphatic amine of carbon number 2 ~ 4, importantly use aliphatic amine that is water-soluble or water dissolvable, specifically, ethamine, n-propylamine, isopropylamine, n-butylamine, isobutyl amine etc. can be used, when considering low-temperature sintering and the treatability of silver-colored microparticle, preferred n-propylamine and n-butylamine.
As the alcohol in solvent reaction system, alcohol having a miscibility with water can be used.Specifically, methyl alcohol, ethanol, propyl alcohol and isopropyl alcohol etc. can be used, be preferably methyl alcohol and ethanol.These alcohol can be used alone also can be used in combination.
Reductant solution in solvent reaction system, can be obtained by mixing by being dissolved in water by ascorbic acid or arabo-ascorbic acid or making ascorbic acid or arabo-ascorbic acid be dissolved in interpolation alcohol after in water.Ascorbic acid or arabo-ascorbic acid are preferably 1.0 ~ 2.0 moles relative to silver nitrate 1 mole, are more preferably 1.0 ~ 1.8 moles.When ascorbic acid or arabo-ascorbic acid relative to silver nitrate 1 mole more than 2.0 moles, the silver-colored microparticle of generation has the trend of aggegation each other, therefore not preferred.
The alcoholic solution of silver salt complex to the interpolation in the reductant solution in solvent reaction system, by the alcoholic solution of above-mentioned silver salt complex being dripped in reducing solution carry out.The reaction temperature of reduction reaction is the scope of 15 ~ 30 DEG C, is more preferably 18 ~ 30 DEG C.When reaction temperature is more than 30 DEG C, crystallite diameter becomes large, therefore not preferred.In addition, rate of addition is preferably less than 3ml/ minute.When time for adding is short, particle size and crystallite diameter have the trend that change is large, not preferably.
After dropping terminates, after continuing stirring more than 1 hour, by leaving standstill, silver-colored microparticle being precipitated, after being removed by supernatant by decant, using alcohol and water to utilize usual method to carry out filtering, washing.Now, carry out cleaning until the electrical conductivity of filtrate becomes 60 below μ S/cm.
By the silver-colored microparticle after cleaning after temperature less than 30 DEG C carries out drying or vacuum drying, utilize usual method to pulverize, silver-colored microparticle of the present invention can be obtained thus.When baking temperature is more than 30 DEG C, the crystallite diameter D of silver-colored microparticle
x(111) become large, and crystallite diameter D
x(111)/crystallite diameter D
x(200) ratio becomes and is less than 1.40, and low-temperature sintering suffers damage, therefore not preferred.
In any manufacture method, all can obtain silver-colored microparticle of the present invention by utilizing usual method to be pulverized by dried silver-colored microparticle.
Silver-colored microparticle of the present invention, preferably utilizes macromolecule dispersing agent to carry out surface treatment in advance before pulverization process.In the 1st aspect of the present invention, be selected from the high score subclass dispersant of number-average molecular weight more than 1000 one kind or two or more is preferably as mentioned above utilized to carry out surface treatment in advance.The covering amount of the macromolecular compound of molecular weight more than 1000, is preferably 0.1 ~ 3.0 % by weight relative to silver-colored microparticle, is more preferably 0.2 ~ 2.5 % by weight.By the treating capacity of macromolecular compound in above-mentioned scope, the sufficient treatment effect of pulverization process can be obtained.In addition, in the 2nd aspect of the present invention, the macromolecular compound of molecular weight more than 10000 is preferably utilized to carry out surface treatment as mentioned above.The covering amount of the macromolecular compound of molecular weight more than 10000, is preferably 0.2 ~ 4 % by weight relative to silver-colored microparticle, is more preferably 0.3 ~ 3 % by weight.By the treating capacity of macromolecular compound in above-mentioned scope, the sufficient treatment effect of pulverization process can be obtained.By utilizing macromolecular compound to carry out surface treatment in advance, high pulverization process effect can be obtained in the pulverization process of carrying out thereafter, can carry out evenly pulverization process.On the other hand, when adding macromolecular compound in the reduction evolution reaction of silver-colored microparticle, the uniformity existing problems for the treatment of capacity and treatment effect, can produce aggegation block in the pulverization process of carrying out thereafter, the silver-colored microparticle obtained is difficult to disperse in conductive paste, therefore not preferred.
In the surface treatment utilizing macromolecular compound to carry out silver-colored microparticle, make to utilize hydrophilic organic solvent to carry out replacing and dried silver-colored microparticle, be redispersed in and macromolecular compound is dissolved in organic solvent and in the macromolecular compound solution obtained, after slowly carrying out stirring for 30 ~ 300 minutes, organic solvent is removed, below 30 DEG C, uses drying machine or vacuum drying to carry out drying.
Utilize macromolecular compound to carry out the pulverizing of the silver-colored microparticle after surface treatment, preferably use jet pulverizer.
Then, the conductive paste containing silver-colored microparticle of the present invention is described.
Conductive paste of the present invention can be fire any form in type cream and polymer-type cream, when firing type cream, comprising silver-colored microparticle of the present invention and frit, can coordinate other compositions such as adhesive resin, solvent as required.In addition, when polymer-type cream, comprise silver-colored microparticle of the present invention and solvent, other compositions such as adhesive resin, curing agent, dispersant, rheology modifier can be coordinated as required.
As adhesive resin, adhesive resin well known in the art can be used in, such as, can enumerate: the cellulosic resin such as ethyl cellulose, nitrocellulose; Mylar; The various modified polyester resins such as urethane modified polyester resin, epoxy modified polyester resin, acrylated polyester; Polyurethane resin; Vinyl chloride vinyl acetate copolymer; Acrylic resin; Epoxy resin; Phenolic resins; Alkyd resins; Butyral resin; Polyvinyl alcohol; Polyimides; Polyamidoimide etc.These adhesive resins can be used alone, or also can and use two or more.
As solvent, solvent well known in the art can be used in, such as, can enumerate: the varsols such as the tetradecane, toluene, dimethylbenzene, ethylbenzene, diethylbenzene, isopropylbenzene, amylbenzene, p-cymene, tetrahydronaphthalene and petroleum-type aromatic hydrocarbon mixture; Ether or the glycol ethers solvents such as ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, dihydroxypropane single-ether, propane diols mono-n-butyl ether, propylene glycol t-butyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, dipropylene glycol methyl ether, dipropylene glycol monobutyl ether, tripropylene glycol methyl ether; The diol-lipid solvents such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethylether acetate, ethylene glycol monomethyl ether acetate, propylene glycol methyl ether acetate, propylene glycol monoethyl ether acetate; The ketones solvent such as methyl iso-butyl ketone (MIBK), cyclohexanone; The terpenols such as terpinol, linalool, geraniol, citronellol; The alcohols solvents such as n-butanol, sec-butyl alcohol, the tert-butyl alcohol; The glycolic solvents such as ethylene glycol, diethylene glycol (DEG); Gamma-butyrolacton and water etc.Solvent can be used alone, or also can and use two or more.
The content of the silver-colored microparticle in conductive paste is different according to purposes, such as, form the situations such as the situation of purposes at distribution under, preferably as far as possible close to 100 % by weight.
Conductive paste of the present invention, by using various mixing roll, the dispersion machines such as mixing and kneading machine, jar mill, three-roller type grinder, rotary mixer, double-shaft mixer, can make each composition mix, disperses and obtain.
Conductive paste of the present invention can be applied to the various coating methods such as serigraphy, ink-jet method, intaglio printing, hectographic printing, roller coat, flow coat, spraying, spin coating, dip-coating, scraper coating, plating.
In addition, conductive paste of the present invention, can as FPD(flat-panel monitor), the electrode of solar cell, organic EL etc. formed and the distribution of LSI substrate is formed and fine groove, through hole, contact hole the distribution to imbed etc. form materials'use.In addition, under the high temperature such as the internal electrode formation of multi-layer ceramic capacitor or laminated inductor, fire purposes much less, because can low-firing, so the distribution be suitable as on flexible base board or IC-card, other substrates forms material and electrode forms material.In addition, also electromagnetic wave proof film and infrared reflection overcoat etc. can be used for as conductive film covering.Also can use as parts installation grafting material in electronic equipment is installed.
< effect >
Importantly following true in the present invention: ratio [the crystallite diameter D of the Miller indices (111) obtained by X-ray diffraction and the crystallite diameter of (200)
x(111)/crystallite diameter D
x(200)] be more than 1.40 silver-colored microparticle can low-firing.And, the average grain diameter (D of this silver-colored microparticle
sEM) be preferably more than 30nm and be less than 1 μm, the average grain diameter of very wide region can be selected.
The reason of silver-colored microparticle low-temperature sintering excellence of the present invention is unclear, but, present inventor has performed a large amount of experiments, found that: the silver-colored microparticle of the agglutinating property excellence under low temperature, ratio [the crystallite diameter D of crystallite diameter
x(111)/crystallite diameter D
x(200) value of more than 1.40] is.Can think and this demonstrate: crystallite diameter D
x(111) with crystallite diameter D
x(200) ratio is larger, and the distortion of lattice is more large more unstable, and silver-colored microparticle is active.
Embodiment
Below, provide embodiments of the invention, the present invention will be described particularly, but the present invention is not limited to following embodiment.In addition, in following example, embodiment 1-1 ~ 1-9, comparative example 1-1 ~ 1-5, embodiment 2-1 ~ 2-9, comparative example 2-1 ~ 2-5, embodiment 3-1 ~ 3-9 and comparative example 3-1 ~ 3-5 are the examples of the 1st aspect of the present invention, and embodiment 4-1 ~ 4-13, comparative example 4-1 ~ 4-7, embodiment 5-1 ~ 5-13 and comparative example 5-1 ~ 5-7 are the examples of the 1st aspect of the present invention.
The average grain diameter of silver microparticle, uses the photo of scanning electron microscope photographic means " S-4800 " (HITACHI manufacture) shooting particle, uses this photo to the particle mensuration particle diameter of more than 100, calculates its mean value, as average grain diameter (D
sEM).
The specific area of silver microparticle, represents by the value using " Monosorb MS-11 " (manufacture of Kang Ta (QUANTACHROME) company) to utilize BET method to measure.
The crystallite diameter D of silver microparticle
xand crystallite diameter D (111)
x(200), use X-ray diffraction device " RINT2500 " (Co., Ltd. Neo-Confucianism (Rigaku Corporation) manufacture), obtain using the K alpha ray of Cu as the radiogenic indices of crystallographic plane (1,1,1) face and (2,0,0) half breadth at the peak in face, utilizes Scherrer formulae discovery crystallite diameter.
The ratio of the Miller indices (111) obtained by X-ray diffraction of silver microparticle and the crystallite diameter of (200), uses above-mentioned crystallite diameter D
xand crystallite diameter D (111)
x(200) by [crystallite diameter D
x(111)/crystallite diameter D
x(200)] obtain.
The rate of change (%) of the crystallite diameter caused by heating of silver microparticle uses silver-colored microparticle at 150 DEG C of heating crystallite diameter D after 30 minutes
x(111) the crystallite diameter D of the silver-colored microparticle and before heating
x(111), according to the value that following formula 1 calculates.In addition, heating condition is being changed into the rate of change obtaining crystallite diameter when heating 30 minutes for 210 DEG C similarly.
< formula 1 >
Crystallite diameter × 100 of the silver-colored microparticle before the crystallite diameter/heating of the silver-colored microparticle after rate of change (the %)=heating of crystallite diameter
Use the characteristic of the conductive coating of type of the firing cream in the example of the 1st aspect of the present invention, obtained by following method.Namely, for the conductive paste firing type described later is coated on aluminum oxide substrate, at 120 DEG C after predrying 30 minutes, at 200 DEG C, 300 DEG C, 400 DEG C, 500 DEG C, 600 DEG C of heating 30 minutes and the conductive film that obtains, use 4 terminal resistance determinators " Loresta GP/MCP-T600 " (Mitsubishi of Co., Ltd. chemical analysis technology (Mitsubishi Chemical Analytech Co., Ltd.) manufacture) measure, resistivity is calculated according to sheet resistance and thickness, using the transverse axis of temperature as chart, layer resistivity is drawn as the longitudinal axis, 1 × 10 is become with layer resistivity
-5the temperature of below Ω cm represents.In addition, the layer resistivity of the conductive film when 120 DEG C, 200 DEG C and 400 DEG C heat 30 minutes is respectively given.
In addition, when polymer-type cream, give and will apply the conductive paste of electric conductive polymer type described later on the polyimide film of thickness 50 μm and the conducting film that obtains, the layer resistivity of the conductive film respectively when 120 DEG C, 210 DEG C and 300 DEG C of heating 30 minutes.
The resistivity of the conductive coating in the example of the 1st aspect of the present invention, for conductive paste described later is coated on polyimide film, after 120 DEG C predrying, each heating temperatures of 150 DEG C, 210 DEG C and 300 DEG C solidify 30 minutes and the conductive film obtained separately, use 4 terminal resistance determinators " Loresta GP/MCP-T600 " (Mitsubishi of Co., Ltd. chemical analysis technology manufactures) to measure, calculate resistivity according to sheet resistance and thickness.
< embodiment 1-1: the manufacture > of silver-colored microparticle
The arabo-ascorbic acid 739g(added in the reaction tower of 50L as reducing agent is 1.5mol relative to silver-colored 1mol), pure water 32.3L and ammoniacal liquor (25%) 780g(is 4.1mol relative to silver-colored 1mol) after, carry out mixing, stirring while being cooled to below 18 DEG C, prepare reducing solution.In addition, add silver nitrate 475g and pure water 6300g in the plastic containers of 20mL after, carry out mixing, stirring while being cooled to below 18 DEG C, prepare silver nitrate aqueous solution.
Then, reaction system is cooled to less than 20 DEG C, and in reducing solution, adds silver nitrate aqueous solution (the interpolation time is 10 seconds below) while stirring.Add after terminating, after stirring 30 minutes, leave standstill and solid content was precipitated in 30 minutes.After being removed by supernatant by decant, use filter paper to carry out suction strainer, then, use pure water to carry out cleaning, filtering, until the electrical conductivity of filtrate becomes 7 μ S/cm.
Make the filter cake of the silver-colored microparticle obtained be redispersed in methanol solution, the moisture of silver-colored microparticle surfaces is replaced into methyl alcohol and filter after, 25 DEG C of dryings 6 hours in vacuum drier.Then, be dispersed in the solution obtained in the mixed solution (water: methyl alcohol than be 1:10) of pure water and methyl alcohol to making 2.4g macromolecular compound " DISPERBYK-106 " (trade name: Bi Ke chemistry Japanese Co., Ltd manufacture), adding the silver-colored microparticle 300g(obtained is 0.8 % by weight relative to silver-colored microparticle), in vacuum drier after 25 DEG C of dryings 12 hours, utilize jet pulverizer to pulverize, obtain the silver-colored microparticle of embodiment 1-1.
The grain shape of the silver-colored microparticle obtained is granular, average grain diameter (D
sEM) be 268nm, crystallite diameter D
x(111) be 14.2nm, crystallite diameter D
x(200) be 9.0nm, D
x(111)/D
x(200) be 1.58, BET specific surface area value is 1.5m
2/ g, the rate of change (150 DEG C × 30 minutes) of crystallite diameter is 128%, and the rate of change (210 DEG C × 30 minutes) of crystallite diameter is 179%.
< embodiment 2-1: manufacture (the firing type cream) > of conductive paste
Relative to silver-colored microparticle 100 weight portion of embodiment 1-1, add ethyl cellulose resin 2.5 weight portion, lead-less glasses material 2.5 weight portion, n-butyl phthalate 3.0 weight portion and 2, 2, 4-trimethyl-1, 3-pentanediol one isobutyl ester (TEXANOL)/1-phenoxy group-2-propyl alcohol (1:1) 15.4 weight portion, (Thinky Corp. (THINKY CORPORATION) manufactures to use rotation-revolution mixer " Awa-tori RENTARO ARE-310 ", registration mark) carry out premixed after, 3 rollers are used to carry out mixing equably, dispersion treatment, obtain the conductive paste (firing type cream) of embodiment 2-1.
To be coated on aluminum oxide substrate by conductive paste obtained above (firing type cream), at 120 DEG C after predrying 30 minutes, 200 DEG C, 300 DEG C, 400 DEG C, 500 DEG C, 600 DEG C heating 30 minutes, obtain conductive coating thus.
The layer resistivity of the conductive coating obtained becomes 1.0 × 10
-5the temperature of below Ω cm is 195 DEG C.In addition, the resistivity of carrying out when heating for 30 minutes at 120 DEG C is 7.7 × 10
-5Ω cm is 9.1 × 10 when 200 DEG C of resistivity of carrying out when heating for 30 minutes
-6Ω cm is 4.7 × 10 when 400 DEG C of resistivity of carrying out when heating for 30 minutes
-6Ω cm.
< embodiment 3-1: manufacture (polymer-type cream) > of conductive paste
Adding mylar 11.0 weight portion and curing agent 1.4 weight portion and diethylene glycol monoethyl ether relative to silver-colored microparticle 100 weight portion of embodiment 1-1 makes the content of the silver-colored microparticle in conductive paste become 70wt%, after carrying out premixed, use 3 rollers to carry out mixing, dispersion treatment equably, obtain the conductive paste of embodiment 3-1.
To be coated on the polyimide film of thickness 50 μm by conductive paste obtained above (polymer-type cream), and heat 30 minutes 120 DEG C, 210 DEG C and 300 DEG C respectively, obtain conductive coating thus.
By the conductive coating obtained when 120 DEG C carry out 30 minutes heat resistivity be 3.7 × 10
-4Ω cm is 2.8 × 10 when 210 DEG C of resistivity of carrying out when heating for 30 minutes
-6Ω cm is 9.8 × 10 when 300 DEG C of resistivity of carrying out when heating for 30 minutes
-6Ω cm.
Silver-colored microparticle and conductive paste is made according to above-described embodiment 1-1, embodiment 2-1 and embodiment 3-1.Provide every characteristic of each manufacturing condition and the silver-colored microparticle powder obtained and conductive paste.
< embodiment 1-2 ~ 1-4 and comparative example 1-1 ~ 1-2 >
By carrying out various change to the formation condition of silver-colored microparticle, obtain silver-colored microparticle.In addition, the particle of comparative example 1-5 is the silver particle powder of commercially available micron-scale.
Manufacturing condition is now shown in table 1, every characteristic of the silver-colored microparticle obtained is shown in table 3.
< embodiment 1-6: the manufacture > of silver-colored microparticle
Adding in the reaction tower of 50L as silver nitrate 595g, the pure water 38L of silver material and ammoniacal liquor (25%) 2381g(relative to silver-colored 1mol is 10.0mol) after, carry out mixing, stirring while being cooled to below 10 DEG C, prepare the silver salt complex aqueous solution.In addition, the arabo-ascorbic acid 925g(added in the plastic containers of 20L as reducing agent is 1.5mol relative to silver-colored 1mol) and pure water 8333g after, carry out mixing, stirring, the aqueous solution of preparation containing reducing agent while being cooled to below 10 DEG C.
Then, reaction system is cooled to less than 10 DEG C, and in the silver salt complex aqueous solution, adds the aqueous solution (the interpolation time is 10 seconds below) containing reducing agent while stirring.Add after terminating, after stirring 30 minutes, leave standstill and solid content was precipitated in 30 minutes.After being removed by supernatant by decant, use filter paper to carry out suction strainer, then, use pure water to carry out cleaning, filtering, until the electrical conductivity of filtrate becomes 20 μ S/cm.
Make the filter cake of the silver-colored microparticle obtained be redispersed in methanol solution, the moisture of silver-colored microparticle surfaces is replaced into methyl alcohol and filter after, 25 DEG C of dryings 6 hours in vacuum drier.Then, be dispersed in the solution obtained in the mixed solution (water: methyl alcohol than be 1:10) of pure water and methyl alcohol to making 3.6g macromolecular compound " DISPERBYK-106 " (trade name: Bi Ke chemistry Japanese Co., Ltd manufacture), adding the silver-colored microparticle 300g(obtained is 1.2 % by weight relative to silver-colored microparticle), in vacuum drier after 25 DEG C of dryings 12 hours, utilize jet pulverizer to pulverize, obtain the silver-colored microparticle of embodiment 1-1.
< embodiment 1-7 ~ 1-9 and comparative example 1-3 ~ 1-4 >
By carrying out various change to the formation condition of silver-colored microparticle, obtain silver-colored microparticle.
Manufacturing condition is now shown in table 2, every characteristic of the silver-colored microparticle obtained is shown in table 3.
[table 3]
The manufacture > of < conductive paste (firing type cream)
< embodiment 2-2 ~ 2-9 and comparative example 2-1 ~ 2-5 >
Except making the kind of silver-colored microparticle carry out except various change, manufacture conductive paste and conductive coating according to the preparation method of the conductive paste (firing type cream) of above-described embodiment 2-1.
Manufacturing condition now and every characteristic of the conductive coating obtained are shown in table 4.
[table 4]
The manufacture > of < conductive paste (polymer-type cream)
< embodiment 3-2 ~ 3-9 and comparative example 3-1 ~ 3-5 >
Except making the kind of silver-colored microparticle carry out except various change, manufacture conductive paste and conductive coating according to the preparation method of the conductive paste (polymer-type cream) of above-described embodiment 3-1.
Manufacturing condition now and every characteristic of the conductive coating obtained are shown in table 5.
[table 5]
< embodiment 4-1: the manufacture > of silver-colored microparticle
The arabo-ascorbic acid 739g(added in the reaction tower of 50L as reducing agent is 1.5mol relative to silver-colored 1mol), pure water 33.4L and ammoniacal liquor (25%) 3808g(is 20mol relative to silver-colored 1mol) after, carry out mixing, stirring while being cooled to below 18 DEG C, prepare reducing solution.In addition, add silver nitrate 475g and pure water 1900g in the plastic containers of 20L after, carry out mixing, stirring while being cooled to below 18 DEG C, prepare silver nitrate aqueous solution.
Then, reaction system is cooled to less than 20 DEG C, and in reducing solution, adds silver nitrate aqueous solution (the interpolation time is 10 seconds below) while stirring.Add after terminating, after stirring 30 minutes, leave standstill and solid content was precipitated in 30 minutes.After being removed by supernatant by decant, use filter paper to carry out suction strainer, then, use pure water to carry out cleaning, filtering, until the electrical conductivity of filtrate becomes 38 μ S/cm.
Make the filter cake of the silver-colored microparticle obtained be redispersed in methanol solution, the moisture of silver-colored microparticle surfaces is replaced into methyl alcohol and filter after, 25 DEG C of dryings 6 hours in vacuum drier.Then, add 4.2g relative to the silver-colored microparticle 300g obtained and be dispersed in macromolecular compound " DISPERBYK-106 " (the Japanese Co., Ltd of trade name: Bi Ke chemistry manufactures) in methanol solution (be 1.4 % by weight relative to silver-colored microparticle), after carrying out stirring in 90 minutes, mixing, by methyl alcohol distillation removing.Then, in vacuum drier after 25 DEG C of dryings 6 hours, utilize jet pulverizer to pulverize, obtain the silver-colored microparticle of embodiment 4-1.
The grain shape of the silver-colored microparticle obtained is granular, average grain diameter (D
sEM) be 86.0nm, crystallite diameter D
x(111) be 15.4nm, crystallite diameter D
x(200) be 9.5nm, D
x(111)/D
x(200) be 1.62, BET specific surface area value is 2.9m
2/ g, the rate of change (150 DEG C × 30 minutes) of crystallite diameter is 118%, and the rate of change (210 DEG C × 30 minutes) of crystallite diameter is 145%.
< embodiment 5-1: the manufacture > of conductive paste
Adding mylar 11.0 weight portion and curing agent 1.4 weight portion and diethylene glycol monoethyl ether relative to silver-colored microparticle 100 weight portion of embodiment 4-1 makes the content of the silver-colored microparticle in conductive paste become 70wt%, (Thinky Corp. manufactures to use rotation-revolution mixer " Awa-tori RENTARO ARE-310 ", registration mark) carry out premixed after, use 3 rollers to carry out mixing, dispersion treatment equably, obtain conductive paste.
To be coated in by conductive paste obtained above on the polyimide film of thickness 50 μm, heat 30 minutes 120 DEG C, 210 DEG C and 300 DEG C respectively, obtain conductive coating thus.
By the conductive coating obtained when 120 DEG C carry out 30 minutes heat resistivity be 1.5 × 10
-5Ω cm is 6.8 × 10 when 210 DEG C of resistivity of carrying out when heating for 30 minutes
-6Ω cm is 3.1 × 10 when 300 DEG C of resistivity of carrying out when heating for 30 minutes
-6Ω cm.
Silver-colored microparticle and conductive paste is made according to above-described embodiment 4-1 and embodiment 5-1.Provide every characteristic of each manufacturing condition and the silver-colored microparticle powder obtained and conductive paste.
< embodiment 4-2 ~ 4-5 and comparative example 4-1 ~ 4-2 >
By carrying out various change to the formation condition of silver-colored microparticle, obtain silver-colored microparticle.
Manufacturing condition is now shown in table 6, every characteristic of the silver-colored microparticle obtained is shown in table 9.
< embodiment 4-6: the manufacture > of silver-colored microparticle
Adding in the reaction tower of 50L as the silver nitrate 475g of silver material and ammoniacal liquor (25%) 3808g(relative to silver-colored 1mol is 20mol) after, carry out mixing, stirring while being cooled to below 8 DEG C, prepare the silver salt complex aqueous solution.In addition, the arabo-ascorbic acid 739g(added in the plastic containers of 20L as reducing agent is 1.5mol relative to silver-colored 1mol) and pure water 3530g after, carry out mixing, stirring while being cooled to below 9 DEG C, the aqueous solution of preparation containing reducing agent.
Then, reaction system is cooled to less than 10 DEG C, and in the silver salt complex aqueous solution, adds the aqueous solution (the interpolation time is 10 seconds below) containing reducing agent while stirring.Add after terminating, after stirring 30 minutes, leave standstill and solid content was precipitated in 30 minutes.After being removed by supernatant by decant, use filter paper to carry out suction strainer, then, use pure water to carry out cleaning, filtering, until the electrical conductivity of filtrate becomes 15 μ S/cm.
Make the filter cake of the silver-colored microparticle obtained be redispersed in methanol solution, the moisture of silver-colored microparticle surfaces is replaced into methyl alcohol and filter after, 25 DEG C of dryings 6 hours in vacuum drier.Then, add 4.2g relative to the silver-colored microparticle 300g obtained and be dispersed in macromolecular compound " DISPERBYK-106 " (the Japanese Co., Ltd of trade name: Bi Ke chemistry manufactures) in methanol solution (be 1.4 % by weight relative to silver-colored microparticle), after carrying out stirring in 90 minutes, mixing, by methyl alcohol distillation removing.Then, in vacuum drier after 25 DEG C of dryings 6 hours, utilize jet pulverizer to pulverize, obtain the silver-colored microparticle of embodiment 4-6.
< embodiment 4-7 ~ 4-9 and comparative example 4-3 ~ 4-4 >
By carrying out various change to the formation condition of silver-colored microparticle, obtain silver-colored microparticle.
Manufacturing condition is now shown in table 7, every characteristic of the silver-colored microparticle obtained is shown in table 9.
< embodiment 4-10: the manufacture > of silver-colored microparticle
Add silver nitrate 160g and methyl alcohol 800mL in the beaker of 2L after, add n-butylamine 151.6g while carrying out cooling with water-bath after, carry out mixing, stirring while being cooled to below 18 DEG C, preparation A liquid.In addition, in the beaker of 5L, measure arabo-ascorbic acid 248.8g, add 1600mL water and carry out stirring and make after it dissolves, to add methyl alcohol 800mL, carry out mixing, stirring while being cooled to less than 18 DEG C, prepare B liquid.
Then, B liquid is stirred, while reaction system being cooled to below 20 DEG C, with 1 hour 20 minutes, A drop is added in B liquid.After dropping terminates, after stirring 14 hours, leave standstill and solid content was precipitated in 30 minutes.After being removed by supernatant by decant, use filter paper to carry out suction strainer, then, use methyl alcohol and pure water to carry out cleaning, filtering.
By the solid content of silver-colored microparticle that obtains in vacuum drier after 30 minutes dry 6 hours, add 0.48g relative to the silver-colored microparticle 24g obtained and be dispersed in macromolecular compound " DISPERBYK-106 " (the Japanese Co., Ltd of trade name: Bi Ke chemistry manufactures) in methanol solution (be 2.0 % by weight relative to silver-colored microparticle), after carrying out stirring in 90 minutes, mixing, by methyl alcohol distillation removing.Then, in vacuum drier after 25 DEG C of dryings 6 hours, utilize jet pulverizer to pulverize, obtain the silver-colored microparticle of embodiment 4-10.
Manufacturing condition is now shown in table 8, every characteristic of the silver-colored microparticle obtained is shown in table 9.
< embodiment 4-11 ~ 4-13 and comparative example 4-5 ~ 4-6 >
By carrying out various change to the formation condition of silver-colored microparticle, obtain silver-colored microparticle.
Manufacturing condition is now shown in table 7, every characteristic of the silver-colored microparticle obtained is shown in table 9.
[table 9]
The manufacture > of < conductive coating paint
< embodiment 5-2 ~ 5-13 and comparative example 5-1 ~ 5-7 >
Except making the kind of silver-colored microparticle carry out except various change, manufacture conductive coating paint and conductive film according to the preparation method of the conductive coating paint of above-described embodiment 5-1.
Manufacturing condition now and every characteristic of the conductive coating obtained are shown in table 10.
[table 10]
Utilizability in industry
Silver-colored microparticle of the present invention, ratio [the crystallite diameter D of the crystallite diameter of the Miller indices obtained by X-ray diffraction (111) and (200)
x(111)/crystallite diameter D
x(200) be] more than 1.40, therefore, being suitable as can the raw material of conductive paste etc. of low-firing.
Claims (12)
1. a silver-colored microparticle, is characterized in that:
The ratio of the Miller indices (111) obtained by X-ray diffraction and the crystallite diameter of (200) is with crystallite diameter D
x(111)/crystallite diameter D
x(200) more than 1.40 are counted.
2. silver-colored microparticle as claimed in claim 1, is characterized in that:
Average grain diameter D
sEM1 μm is less than for more than 100nm.
3. silver-colored microparticle as claimed in claim 1 or 2, is characterized in that:
The crystallite diameter D of Miller indices (111)
x(111) be below 20nm.
4. silver-colored microparticle as claimed in claim 1 or 2, is characterized in that:
The crystallite diameter D of Miller indices (200)
x(200) be below 14nm.
5. silver-colored microparticle as claimed in claim 1 or 2, is characterized in that:
The particle surface of silver microparticle is one kind or two or more coated by what be selected from the high score subclass dispersant of number-average molecular weight more than 1000.
6. silver-colored microparticle as claimed in claim 1, is characterized in that:
Average grain diameter D
sEM100nm is less than for more than 30nm.
7. the silver-colored microparticle as described in claim 1 or 6, is characterized in that:
The crystallite diameter D of Miller indices (111)
x(111) be below 25nm.
8. the silver-colored microparticle as described in claim 1 or 6, is characterized in that:
The crystallite diameter D of Miller indices (200)
x(200) be below 15nm.
9. the silver-colored microparticle as described in claim 1 or 6, is characterized in that:
The particle surface of silver microparticle is coated by the macromolecular compound of molecular weight more than 10000.
10. a conductive paste, is characterized in that:
Containing the silver-colored microparticle according to any one of claim 1 ~ 9.
11. 1 kinds of conductive films, is characterized in that:
The conductive paste described in claim 10 is used to be formed.
12. 1 kinds of electronic devices, is characterized in that:
There is conductive film according to claim 11.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011-167368 | 2011-07-29 | ||
| JP2011167364A JP5773147B2 (en) | 2011-07-29 | 2011-07-29 | Silver fine particles, and conductive paste, conductive film and electronic device containing the silver fine particles |
| JP2011167368A JP5773148B2 (en) | 2011-07-29 | 2011-07-29 | Silver fine particles, and conductive paste, conductive film and electronic device containing the silver fine particles |
| JP2011-167364 | 2011-07-29 | ||
| PCT/JP2012/068939 WO2013018645A1 (en) | 2011-07-29 | 2012-07-26 | Fine silver particles, conductive paste containing fine silver particles, conductive film and electronic device |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103702786A CN103702786A (en) | 2014-04-02 |
| CN103702786B true CN103702786B (en) | 2015-07-29 |
Family
ID=47629170
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201280036601.7A Expired - Fee Related CN103702786B (en) | 2011-07-29 | 2012-07-26 | Silver microparticle and the conductive paste containing this silver-colored microparticle, conductive film and electronic device |
Country Status (4)
| Country | Link |
|---|---|
| KR (1) | KR20140047663A (en) |
| CN (1) | CN103702786B (en) |
| TW (1) | TW201315685A (en) |
| WO (1) | WO2013018645A1 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6530709B2 (en) | 2014-03-05 | 2019-06-12 | 積水化学工業株式会社 | Conductive filler, method of producing conductive filler and conductive paste |
| JP6948764B2 (en) * | 2015-06-05 | 2021-10-13 | Ｄｏｗａエレクトロニクス株式会社 | Silver fine particle dispersion |
| JP2018165387A (en) * | 2017-03-28 | 2018-10-25 | Ｄｏｗａエレクトロニクス株式会社 | Bonding material and bonding body comprising the same |
| CN108650873B (en) * | 2018-05-15 | 2021-03-02 | 河南科技大学第一附属医院 | Environment-friendly device for eliminating radiation hazard of nuclear magnetic resonance to human body |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005149913A (en) * | 2003-11-14 | 2005-06-09 | Mitsui Mining & Smelting Co Ltd | Silver paste and its manufacturing method |
| CN1700360A (en) * | 2004-05-19 | 2005-11-23 | 同和矿业株式会社 | Spherical silver powder and method for producing same |
| JP2006040650A (en) * | 2004-07-26 | 2006-02-09 | Mitsui Mining & Smelting Co Ltd | Silver paste and its manufacturing method |
| CN1826197A (en) * | 2003-07-29 | 2006-08-30 | 三井金属矿业株式会社 | Fine-grain silver powder and process for producing the same |
| JP2007077479A (en) * | 2005-09-16 | 2007-03-29 | Dowa Holdings Co Ltd | Composite particle powder, dispersion liquid or paste thereof and production method therefor |
| WO2011040521A1 (en) * | 2009-10-02 | 2011-04-07 | 戸田工業株式会社 | Fine silver particles, method for producing same, conductive paste containing the fine silver particles, conductive film, and electronic device |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5252843B2 (en) * | 2007-01-09 | 2013-07-31 | Ｄｏｗａエレクトロニクス株式会社 | Silver ink and its manufacturing method |
| JP5190420B2 (en) * | 2009-07-16 | 2013-04-24 | 株式会社ノリタケカンパニーリミテド | Silver fine particles and method for producing the same |
| JP5715355B2 (en) * | 2010-08-11 | 2015-05-07 | 三井金属鉱業株式会社 | Flat silver particles and method for producing the same |
-
2012
- 2012-07-26 CN CN201280036601.7A patent/CN103702786B/en not_active Expired - Fee Related
- 2012-07-26 KR KR1020147001483A patent/KR20140047663A/en not_active Application Discontinuation
- 2012-07-26 WO PCT/JP2012/068939 patent/WO2013018645A1/en active Application Filing
- 2012-07-27 TW TW101127260A patent/TW201315685A/en unknown
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1826197A (en) * | 2003-07-29 | 2006-08-30 | 三井金属矿业株式会社 | Fine-grain silver powder and process for producing the same |
| JP2005149913A (en) * | 2003-11-14 | 2005-06-09 | Mitsui Mining & Smelting Co Ltd | Silver paste and its manufacturing method |
| CN1700360A (en) * | 2004-05-19 | 2005-11-23 | 同和矿业株式会社 | Spherical silver powder and method for producing same |
| JP2006040650A (en) * | 2004-07-26 | 2006-02-09 | Mitsui Mining & Smelting Co Ltd | Silver paste and its manufacturing method |
| JP2007077479A (en) * | 2005-09-16 | 2007-03-29 | Dowa Holdings Co Ltd | Composite particle powder, dispersion liquid or paste thereof and production method therefor |
| WO2011040521A1 (en) * | 2009-10-02 | 2011-04-07 | 戸田工業株式会社 | Fine silver particles, method for producing same, conductive paste containing the fine silver particles, conductive film, and electronic device |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20140047663A (en) | 2014-04-22 |
| TW201315685A (en) | 2013-04-16 |
| CN103702786A (en) | 2014-04-02 |
| WO2013018645A1 (en) | 2013-02-07 |
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