CN103702786A - Fine silver particles, conductive paste containing fine silver particles, conductive film and electronic device - Google Patents
Fine silver particles, conductive paste containing fine silver particles, conductive film and electronic device Download PDFInfo
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- CN103702786A CN103702786A CN201280036601.7A CN201280036601A CN103702786A CN 103702786 A CN103702786 A CN 103702786A CN 201280036601 A CN201280036601 A CN 201280036601A CN 103702786 A CN103702786 A CN 103702786A
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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
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Abstract
Provided are: fine silver particles suitable as a starting material for, e.g., a conductive paste which can be baked at a low temperature; a conductive paste containing said fine silver particles; a conductive film; and an electronic device. The fine silver particles according to the present invention are characterized by showing a ratio of the crystalline diameter at a Miller index in X-ray diffractometry of (111) to the crystalline diameter at a Miller index in X-ray diffractometry of (200) [crystalline diameter DX (111)/crystalline diameter DX (200)] of 1.40 or greater.
Description
Technical field
The present invention relates to be suitable as that the raw material of conductive paste that can low-firing is used, average grain diameter for 100nm is above or average grain diameter is less than silver-colored microparticle and the conductive paste that contains this silver microparticle, conductive film and the electronic device of 100nm.
Background technology
The electrode of electronic device or the formation of circuit pattern, the conductive paste that contains metallic particles by use on substrate, print electrode or circuit pattern after, heat to fire and make the metallic particles sintering containing in conductive paste and carry out, according to heating firing temperature, can be categorized as and fire type cream and polymer-type cream.In recent years, the trend of this heating firing temperature in low temperature.
The type cream of firing is generally used in ceramic substrate, usings metallic particles and frit, solvent etc. as main component, and its heating firing temperature is more than approximately 500 ℃.On the other hand, polymer-type cream is used in film distributing board or conductive adhesive etc., by metallic particles, be dispersed in resin, curing agent, organic solvent, dispersant etc. and the cream obtaining forms, utilize serigraphy etc. this conductive paste to be formed on substrate to the conductive pattern of regulation, until the temperature of 250 ℃ of left and right heat and fire and use.
As above-mentioned metallic particles, can use copper powder and silver powder, especially, the serigraphy of using in the circuit formation of film distributing board, with in conductive paste, is used silver as conductive particle.Although silver has the shortcoming of easy generation migration, compare with the copper with the resistivity of same degree and be difficult to oxidation, therefore easily process, utilized widely.
In recent years, the trend of the heating firing temperature of conductive paste in low temperature.For example, installation base plate as electronic device, generally can be heated to 300 ℃ of left and right, excellent heat resistance, therefore, is used the flexible base, board of polyimides system, but expensive, therefore, recently, studied and used more cheap PET(PETG) substrate or PEN(PEN) substrate material instead.But pet substrate or PEN substrate are compared with the flexible base, board of polyimides system, heat resistance is low, and especially, the PET film substrate using in film distributing board need to heat and fire below at 150 ℃.
In addition, if can heat and fire in the temperature lower than 200 ℃, so also can on the substrate of Merlon or paper etc., form electrode or circuit pattern, can expect the purposes expansion of various electrode materials etc.
As the metallic particles of raw material that can carry out 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 compares with metal derby, and fusing point reduces far away, therefore, can make in low temperature its sintering.
In addition, the silver-colored microparticle of nanometer scale, also as having utilized the lead-free solder that can maintain in low-temperature sintering and when once sintered the character that heat resistance scolder such, in the past do not have to replace material to be expected.
Up to the present, as the wiring material of electronic device or the silver-colored microparticle of electrode material, and silver-colored microparticle that can low-firing, proposed the silver-colored microparticle of submicron-scale to micron-scale, known have: crystallite diameter has been carried out to the spherical silver powder (patent documentation 1) of restriction with respect to the ratio of BET specific area; Average grain diameter, crystallite diameter and average grain diameter have been carried out to the silver-colored microparticle (patent documentation 2) limiting with respect to crystallite diameter ratio; Tap density, laser diffractometry average grain diameter and specific area have been carried out to the silver powder (patent documentation 3) limiting; The average grain diameter of primary particle is the manufacture method (patent documentation 4) of 0.05～1.0 μ m and the crystallite diameter silver-colored microparticle that is 20～150nm; Average grain diameter is that 0.1 μ m is above and be less than 1 μ m and size distribution is precipitous and dispersed high spherical silver powder (patent documentation 5); Primary particle diameter is that 0.07～4.5 μ m and crystallite diameter are high crystallization silver powder (patent documentation 6) more than 20nm; Contain to the temperature range of silver-colored reaction process carried out restriction, primary particle diameter is at composition (patent documentation 7) of the small silver-colored particle of 1～100nm scope etc.
Prior art document
Patent documentation
Patent documentation 1: TOHKEMY 2005-330529 communique
Patent documentation 2: TOHKEMY 2006-183072 communique
Patent documentation 3: TOHKEMY 2007-131950 communique
Patent documentation 4: TOHKEMY 2008-31526 communique
Patent documentation 5: TOHKEMY 2010-70793 communique
Patent documentation 6: TOHKEMY 2007-16258 communique
Patent documentation 7: TOHKEMY 2009-120949 communique
Summary of the invention
The technical problem that invention will solve
Above-mentioned patent documentation 1 is to disclosed silver-colored microparticle in patent documentation 6, all define average grain diameter and crystallite diameter, BET specific area value etc., but all do not consider the Miller indices (111) that obtain by X-ray diffraction and crystallite diameter ratio [the crystallite diameter D of (200)
x(111)/crystallite diameter D
x(200)], as described later shown in comparative example, at above-mentioned crystallite diameter D
x(111)/crystallite diameter D
x(200)] be less than in 1.40 situation, be difficult to obtain having the silver-colored microparticle of good low-temperature sintering.In addition, at crystallite diameter D
x(111) surpass in the situation of 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 is to provide and is suitable as the silver-colored microparticle that the raw material of conductive paste that can low-firing is used.In addition, the object of the invention is to obtain: the average grain diameter of the silver-colored microparticle obtaining is wide region, be particularly preferably 30nm above and be less than 100nm and 100nm above and be less than the silver-colored microparticle of 1 μ m.
Means for technical solution problem
Above-mentioned technical problem can solve by the present invention as described below.
That is, the present invention is a kind of silver-colored microparticle, it is characterized in that the crystallite diameter ratio of the Miller indices that obtain by X-ray diffraction (111) and (200) [crystallite diameter D
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) for 100nm is above and be less than 1 μ m(the present invention 2).
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 20nm following (the present invention 3).
In addition, the present invention is the silver-colored microparticle as described in any one in the present invention 1～3, it is characterized in that the crystallite diameter D of Miller indices (200)
x(200) be 14nm following (the present invention 4).
In addition, the present invention is the silver-colored microparticle as described in any one in 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 more than 1000 high score subclass dispersant of number-average molecular weight.
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 30nm is above 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 25nm following (the present invention 7).
In addition, the present invention is the silver-colored microparticle as described in any one in the present invention 1,6 and 7, it is characterized in that the crystallite diameter D of Miller indices (200)
x(200) be 15nm following (the present invention 8).
In addition, the present invention is the silver-colored microparticle as described in any one in the present invention 1 and 6～8, it is characterized in that, the particle surface of silver-colored microparticle is more than 10000 macromolecular compound coated (the present invention 9) by molecular weight.
In addition, the present invention is a kind of conductive paste, it is characterized in that, contains the silver-colored microparticle described in any one (the present invention 10) in 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, the crystallite diameter ratio of the Miller indices that obtain by X-ray diffraction (111) and (200) [crystallite diameter D
x(111)/crystallite diameter D
x(200) be] more than 1.40, therefore, be suitable as the raw material of conductive paste etc. that can low-firing.
The specific embodiment
Technical scheme of the present invention is described as follows in more detail.
First, silver-colored microparticle of the present invention is described.
Silver-colored microparticle of the present invention is characterised in that, the crystallite diameter ratio of the Miller indices that obtain by X-ray diffraction (111) and (200) [crystallite diameter D
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 be determined according to needed condition in purposes in wide region, from the viewpoint of manufacture method, can be categorized as average grain diameter (D
sEM) be situation and the average grain diameter (D of 100nm above (first method)
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 100nm above and be less than 1 μ m, more preferably 100～500nm.By average grain diameter (D
sEM) in above-mentioned scope, easily tackle becoming more meticulous of distribution and electrode.At average grain diameter (D
sEM) be less than in the situation of 100nm, even also easily there is sintering at normal temperature, in addition, the dispersiveness in conductive paste and the dispersion stabilization trend in reducing, therefore, has the situation that needs such scheme of recording in second method.At average grain diameter (D
sEM) surpass in the situation of 1 μ m, the agglutinating property under low temperature reduces, therefore not preferred.In addition, because particle size is excessive, so use the becoming more meticulous of electronic device that this silver microparticle obtains to become difficult.
Crystallite diameter ratio [the crystallite diameter D of the Miller indices that obtain by X-ray diffraction (111) of the silver-colored microparticle of first method of the present invention and (200)
x(111)/crystallite diameter D
x(200) be] more than 1.40, be preferably more than 1.44, 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 access the silver-colored microparticle of low-temperature sintering excellence.
The crystallite diameter D of the Miller indices that obtain by X-ray diffraction (111) of the silver-colored microparticle of first method of the present invention
x(111) be preferably below 20nm 10～19nm more preferably, further 10～18nm more preferably.At crystallite diameter D
x(111) surpass in the situation of 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) be less than in the situation of 10nm, silver-colored microparticle becomes unstable, even also partly start to occur sintering, welding at normal temperature, therefore not preferred.
The crystallite diameter D of the Miller indices that obtain by X-ray diffraction (200) of the silver-colored microparticle of first method of the present invention
x(200) be preferably below 14nm, more preferably below 13nm, further more preferably below 12nm.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 first method of the present invention, utilize the rate of change [(the crystallite diameter of the silver-colored microparticle before the crystallite diameter/heating of the silver-colored microparticle 150 ℃ of heating after 30 minutes) * 100] of the crystallite diameter being caused by heating described later to evaluate, the rate of change of the crystallite diameter being caused by the heating of 150 ℃ is preferably more than 120%, more preferably more than 125%.In the situation that the rate of change of crystallite diameter is less than 120%, be difficult to low-temperature sintering excellence.In the present invention, 210 ℃ of heating, the in the situation that of 30 minutes, the rate of change of crystallite diameter is preferably more than 150%, more preferably more than 170%.
The BET specific area value of the silver-colored microparticle of first method of the present invention is preferably 5m
2below/g.In BET specific area value, surpass 5m
2in the situation of/g, use the viscosity of the conductive paste that this silver microparticle obtains to uprise, therefore not preferred.
Average grain diameter (the D of the silver-colored microparticle of second method of the present invention
sEM) be less than 100nm, be preferably 30nm above and be less than 100nm, more preferably 35nm is above and be less than 100nm.By average grain diameter (D
sEM) in above-mentioned scope, use the becoming more meticulous of electronic device that this silver microparticle obtains to become easy.At average grain diameter (D
sEM) be less than in the situation of 30nm, the surface-active that silver-colored microparticle has uprises, and in order stably to maintain its fine particle diameter, need to make a large amount of organic matter etc. adhere to, therefore not preferred.
Crystallite diameter ratio [the crystallite diameter D of the Miller indices that obtain by X-ray diffraction (111) of the silver-colored microparticle of second method of the present invention and (200)
x(111)/crystallite diameter D
x(200) be] more than 1.40, be preferably more than 1.44, 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 access the silver-colored microparticle of low-temperature sintering excellence.
The crystallite diameter D of the Miller indices that obtain by X-ray diffraction (111) of the silver-colored microparticle of second method of the present invention
x(111) be preferably below 25nm 23～10nm more preferably, further 20～10nm more preferably.At crystallite diameter D
x(111) surpass in the situation of 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) be less than in the situation of 10nm, silver-colored microparticle becomes unstable, even also partly start to occur sintering, welding at normal temperature, therefore not preferred.
The crystallite diameter D of the Miller indices that obtain by X-ray diffraction (200) of the silver-colored microparticle of second method of the present invention
x(200) be preferably below 15nm, more preferably below 14nm, further more preferably below 13nm.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 second method of the present invention, utilize the rate of change [(the crystallite diameter of the silver-colored microparticle before the crystallite diameter/heating of the silver-colored microparticle 150 ℃ of heating after 30 minutes) * 100] of the crystallite diameter being caused by heating described later to evaluate, the rate of change of the crystallite diameter being caused by the heating of 150 ℃ is preferably more than 150%, more preferably more than 160%.In the situation that the rate of change of crystallite diameter is less than 150%, be difficult to low-temperature sintering excellence.In the present invention, 210 ℃ of heating, the in the situation that of 30 minutes, the rate of change of crystallite diameter is preferably more than 180%, more preferably more than 200%.
The BET specific area value of the silver-colored microparticle of second method of the present invention is preferably 10m
2below/g, 8m more preferably
2below/g.In BET specific area value, surpass 10m
2in the situation of/g, use the viscosity of the conductive paste that this silver microparticle obtains to uprise, therefore not preferred.
The grain shape of the silver-colored microparticle of first method of the present invention and second method, is preferably spherical or granular.
Silver-colored microparticle of the present invention is preferably by one kind or two or more being coated being selected from high score subclass dispersant.In the silver-colored microparticle of first method of the present invention and the silver-colored microparticle of second method, high score subclass dispersant is preferably used according to number-average molecular weight difference.
The silver-colored microparticle of first method of the present invention, the particle surface of preferred silver-colored microparticle is by one kind or two or more being coated being selected from the more than 1000 high score subclass dispersant of number-average molecular weight.The number-average molecular weight of dispersant is preferably more than 1000, and more preferably 1000～150000, further more preferably 5000～100000.By number-average molecular weight, be less than 1000 dispersant and carry out surface-treated silver microparticle powder, the effect of processing with dispersant is insufficient, and in pulverization process thereafter, silver-colored microparticle has the trend of aggegation.On the other hand, in the situation that number-average molecular weight surpasses 150000, the viscosity of dispersant uprises, and is difficult to silver-colored microparticle surface to be processed uniformly.
The silver-colored microparticle of second method of the present invention, by molecular weight, more than 10000 macromolecular compound (high score subclass dispersant) is coated the particle surface of preferred silver-colored microparticle.In the situation that molecular weight is less than 10000, in the pulverization process of carrying out thereafter, can produce aggegation piece, the silver-colored microparticle obtaining is difficult to disperse in conductive paste, therefore not preferred.In addition, on the molecular weight of high score subclass dispersant, be limited to 100000 left and right, when molecular weight is higher than prescribing a time limit on this, viscosity uprises, and is difficult to silver-colored microparticle surface to be processed uniformly.
In the situation of the high score subclass dispersant of any molecular weight of stating in the use, when considering macromolecular compound to the uniformity of the processing on silver-colored microparticle surface and treatment effect, as dispersant, preferably there is (thering is acidic functionality and the 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 according to the BET surface area values of silver-colored microparticle and difference is preferably 0.1～3.0 % by weight with respect to silver-colored microparticle powder, 0.2～2.5 % by weight more preferably.In the situation that 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.In the situation that surpassing 3.0 % by weight, although can suppress the aggegation of silver-colored microparticle powder, the organic components irrelevant with electric conductivity increases, therefore not preferred.
As above-mentioned high score subclass dispersant, can use generally as the commercially available material of pigment dispersing agent, particularly, 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.) manufacture), 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 (the Lubrizol Corporation of Co., Ltd., 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 be used a kind or two or more is used in combination.
Then, the manufacture method of silver-colored microparticle of the present invention is described.
Silver-colored microparticle of the present invention, can obtain by following any manufacture method: to the manufacture method of adding the aqueous solution that contains reducing agent in the aqueous solution that contains silver salt complex and make the silver-colored microparticle that silver-colored microparticle reduction separates out; Or to the manufacture method of adding silver nitrate aqueous solution in reducing solution and make the silver-colored microparticle that silver-colored microparticle reduction separates out.In addition, as the average grain diameter (D of second method of the present invention
sEM) be less than the manufacture method of the silver-colored microparticle of 100nm, also can adopt the manufacture method that makes the silver-colored microparticle of the solvent reaction system that silver-colored microparticle reduction separates out to the alcoholic solution that adds silver salt complex in reductant solution.In any case, importantly in the temperature range below 30 ℃, carry out from being reacted to dry whole operations.
In the situation that to the manufacture method of adding the aqueous solution that contains reducing agent in the aqueous solution that contains silver salt complex and make the silver-colored microparticle that silver-colored microparticle reduction separates out, the previously prepared aqueous solution that contains silver salt complex and the aqueous solution that contains reducing agent respectively.
Silver salt complex in the present invention, can be by being obtained by mixing the silver nitrate as silver material or silver acetate and ammoniacal liquor, ammonium salt or chelate compound etc.As the addition of ammonia, because the ligancy of the ammonia in amine complex is 2, so, preferably with respect to 1 mole of silver, add 2 moles of above ammonia.During the improving of the size distribution of the silver-colored microparticle of considering production stability and obtaining, the addition of ammonia is more preferably more than 4 moles with respect to every 1 moles of silver, further more preferably more than 10 moles.
As the reducing agent in the present invention, can use and be selected from one kind or two or more in arabo-ascorbic acid, ascorbic acid, alkanolamine, quinhydrones, glucose, pyrogallol, hydrazine, hydrogen peroxide and formaldehyde.The viewpoint that dispersiveness from the silver-colored microparticle that makes to obtain conductive paste improves, is preferably used organic reducing agent, more preferably arabo-ascorbic acid or ascorbic acid.
The addition of reducing agent, preferably adds more than 1.0 moles more preferably 1.0～2.0 moles with respect to 1 mole of silver.Especially, in the situation that using ascorbic acid or arabo-ascorbic acid as reducing agent, in the situation that surpassing 2.0 moles with respect to 1 mole of interpolation of silver, the silver-colored microparticle of generation has the trend of aggegation each other, therefore not preferred.
In the situation that to the manufacture method of adding silver nitrate aqueous solution in reducing solution and make the silver-colored microparticle that silver-colored microparticle reduction separates out, also distinguish previously prepared reducing solution and silver nitrate aqueous solution.
Silver nitrate aqueous solution in the present invention, can be 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, more preferably 0.1～1.8mol/l.
Reducing solution can obtain by ammoniacal liquor and ion exchange water or pure water and reducing agent being mixed, stirring.In addition,, as the reducing agent using in reducing solution, can use above-mentioned reducing agent.
The addition of reducing agent, preferably adds more than 1.0 moles more preferably 1.0～2.0 moles with respect to 1 mole of silver.Especially, in the situation that using ascorbic acid or arabo-ascorbic acid as reducing agent, in the situation that surpassing 2.0 moles with respect to 1 mole of interpolation of silver, the silver-colored microparticle of generation has the trend of aggegation each other, therefore not preferred.
When the aqueous solution that contains silver salt complex in preparation, the aqueous solution that contains reducing agent, reducing solution and silver nitrate aqueous solution, preferably liquid temperature is remained on below 18 ℃, when the aqueous solution that contains silver salt complex and the aqueous solution that contains reducing agent or reducing solution and silver nitrate aqueous solution are mixed, stirred, also preferably adjust and make liquid temperature be no more than 20 ℃.In the situation that reaction temperature surpasses 20 ℃, 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 interpolation of the aqueous solution that contains reducing agent in to the interpolation in the aqueous solution that contains silver salt complex or silver nitrate aqueous solution to reducing solution, preferably carries out in the short as far as possible time, in more preferably 20 seconds, further in more preferably 15 seconds.When the aqueous solution that contains reducing agent is to the interpolation time in the aqueous solution that contains silver salt complex or silver nitrate aqueous solution when elongated to the interpolation time in reducing solution, the silver-colored microparticle generating produces aggegation each other, it is large that particle size becomes, and size distribution is in becoming large trend.
Add the aqueous solution that contains reducing agent in the aqueous solution that contains silver salt complex after or add silver nitrate aqueous solution in reducing solution after, stir lentamente, mix the silver-colored microparticle not aggegation each other that makes generation, then, utilize usual method to filter, wash.Now, clean until the electrical conductivity of filtrate becomes below 60 μ S/cm.
Make the filter cake of the silver-colored microparticle that obtains be dispersed in again in hydrophilic organic solvent, after the moisture on silver-colored microparticle surface is replaced into hydrophilic organic solvent, utilize usual method to filter, the silver-colored microparticle obtaining is dried at 30 ℃ of following use drying machines of temperature or vacuum drying.In the situation that baking temperature surpasses 30 ℃, 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 on silver-colored microparticle surface is replaced into hydrophilic organic solvent, can prevent that dried silver-colored microparticle is each the state of firmly aggegation, it is easy that pulverization process thereafter or surface treatment, pulverization process etc. become.
As hydrophilic organic solvent, can use the alcohol such as methyl alcohol, ethanol, propyl alcohol and acetone etc.When consideration is removed solvent by being dried, particular methanol and ethanol.
Utilize the manufacture method of above-mentioned water-based reaction system, can manufacture the silver-colored microparticle of the average grain diameter of the any-mode in first method and second method, as the method for controlling particle diameter, can enumerate the concentration adjustment of the silver nitrate in silver nitrate aqueous solution, the concentration adjustment of the ammoniacal liquor in reducing solution.For example, by the concentration of the silver nitrate in silver nitrate aqueous solution is improved, the concentration of the ammoniacal liquor in reducing solution is reduced, can manufacture the silver-colored microparticle of the average grain diameter that is mainly first method, on the contrary, by the concentration of the silver nitrate in silver nitrate aqueous solution is reduced, the concentration of the ammoniacal liquor in reducing solution is improved, can manufacture the silver-colored microparticle of the average grain diameter that is mainly second method.
To the alcoholic solution that adds silver salt complex in reductant solution, make the alcoholic solution of the silver salt complex in solvent reaction system that silver-colored microparticle reduction separates out, the aliphatic amine of carbon number 2～4 that can be by the silver of mixed nitrate in alcoholic solution and more than a kind water-soluble or water dissolvable obtains.Aliphatic amine is preferably 2.0～2.5 moles with respect to 1 mole of silver nitrate, more preferably 2.0～2.3 moles.In the situation that the amount of aliphatic amine is less than 2.0 moles with respect to 1 mole of silver nitrate, there is the trend of the particle that easy generation is large.
Aliphatic amine as carbon number 2～4, importantly use the aliphatic amine of water-soluble or water dissolvable, particularly, can use ethamine, n-propylamine, isopropylamine, n-butylamine, isobutyl amine etc., while considering the low-temperature sintering of silver-colored microparticle and treatability, preferably n-propylamine and n-butylamine.
As the alcohol in solvent reaction system, can use alcohol having a miscibility with water.Particularly, methyl alcohol, ethanol, propyl alcohol and isopropyl alcohol etc. be can use, methyl alcohol and ethanol are preferably.These alcohol can be used separately also can mix use.
Reductant solution in solvent reaction system, can be by being dissolved in water by ascorbic acid or arabo-ascorbic acid or making ascorbic acid or arabo-ascorbic acid adds alcohol after being dissolved in water and is obtained by mixing.Ascorbic acid or arabo-ascorbic acid are preferably 1.0～2.0 moles with respect to 1 mole of silver nitrate, more preferably 1.0～1.8 moles.In the situation that ascorbic acid or arabo-ascorbic acid surpass 2.0 moles with respect to 1 mole of silver nitrate, the silver-colored microparticle of generation has the trend of aggegation each other, therefore not preferred.
The alcoholic solution of silver salt complex is to the interpolation in the reductant solution in solvent reaction system, by the alcoholic solution of above-mentioned silver salt complex is carried out to dripping in reducing solution.The reaction temperature of reduction reaction is the scope of 15～30 ℃, more preferably 18～30 ℃.In the situation that reaction temperature surpasses 30 ℃, it is large that crystallite diameter becomes, therefore not preferred.In addition, rate of addition was preferably below 3ml/ minute.In the situation that time for adding is short, particle size and crystallite diameter have the trend that becomes large, not preferred.
After dropping finishes, continue to stir 1 hour above after, by standing, silver-colored microparticle is precipitated, after by decant, supernatant being removed, use alcohol and water to utilize usual method to filter, wash.Now, clean until the electrical conductivity of filtrate becomes below 60 μ S/cm.
By the silver-colored microparticle after cleaning 30 ℃ of temperature be dried below or vacuum drying after, utilize usual method to pulverize, can access thus silver-colored microparticle of the present invention.In the situation that baking temperature surpasses 30 ℃, 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 be by utilizing usual method that dried silver-colored microparticle is pulverized and obtained silver-colored microparticle of the present invention.
Silver-colored microparticle of the present invention preferably utilizes in advance macromolecule dispersing agent to carry out surface treatment before pulverization process.In first method of the present invention, preferably utilize in advance to be as mentioned above selected from one kind or two or more in the more than 1000 high score subclass dispersant of number-average molecular weight and to carry out surface treatment.The covering amount of more than 1000 macromolecular compound of molecular weight, is preferably 0.1～3.0 % by weight with respect to silver-colored microparticle, more preferably 0.2～2.5 % by weight.Treating capacity by macromolecular compound, in above-mentioned scope, can access the sufficient treatment effect of pulverization process.In addition, in second method of the present invention, preferably utilize as mentioned above more than 10000 macromolecular compound of molecular weight to carry out surface treatment.The covering amount of more than 10000 macromolecular compound of molecular weight, is preferably 0.2～4 % by weight with respect to silver-colored microparticle, more preferably 0.3～3 % by weight.Treating capacity by macromolecular compound, in above-mentioned scope, can access the sufficient treatment effect of pulverization process.By utilizing macromolecular compound to carry out in advance surface treatment, in the pulverization process of carrying out thereafter, can obtain high pulverization process effect, can carry out more uniform pulverization process.On the other hand, in the situation that add 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 piece in the pulverization process of carrying out thereafter, the silver-colored microparticle obtaining is difficult to disperse in conductive paste, therefore not preferred.
Utilize in the surface treatment that macromolecular compound carries out silver-colored microparticle, make to utilize hydrophilic organic solvent to be replaced and dried silver-colored microparticle, be dispersed in again and macromolecular compound be dissolved in organic solvent and in the macromolecular compound solution obtaining, after slowly carrying out stirring for 30～300 minutes, organic solvent is removed, at 30 ℃ of following use drying machines or vacuum drying, be dried.
Utilize macromolecular compound to carry out the pulverizing of the silver-colored microparticle after surface treatment, preferably use jet pulverizer.
Then, the conductive paste that contains silver-colored microparticle of the present invention is described.
Conductive paste of the present invention can be any form of firing in type cream and polymer-type cream, in the situation that firing type cream, comprises silver-colored microparticle of the present invention and frit, can coordinate other compositions such as adhesive resin, solvent as required.In addition, the in the situation that of polymer-type cream, comprise silver-colored microparticle of the present invention and solvent, can coordinate other compositions such as adhesive resin, curing agent, dispersant, rheology modifier as required.
As adhesive resin, can use at adhesive resin well known in the art, for example, can enumerate: the cellulosic resins such as ethyl cellulose, nitrocellulose; Mylar; The various modified polyester resins such as urethane modified polyester resin, epoxy modified polyester resin, acrylic acid modified 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 separately, or also can and use two or more.
As solvent, can use at solvent well known in the art, for example, 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, the tertiary butyl ether of propane diols list, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monomethyl 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 separately, or also can and use two or more.
The content of the silver-colored microparticle in conductive paste according to purposes and difference, such as forming in the situations such as situation of purposes at distribution, preferably approaches 100 % by weight as far as possible.
Conductive paste of the present invention, can, by using various mixing rolls, the dispersion machines such as mixing and kneading machine, jar mill, three-roller type grinder, rotary mixer, double-shaft mixer, make each composition mix, disperse 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 be as FPD(flat-panel monitor), the electrode of solar cell, organic EL etc. forms and the distribution of LSI substrate forms and the distribution of imbedding etc. of fine groove, through hole, contact hole forms materials'use.In addition, the internal electrode of multi-layer ceramic capacitor or laminated inductor forms with waiting and fires purposes much less under high temperature, because can low-firing, so be suitable as distribution formation material and the electrode formation material on flexible base, board or IC-card, other substrates.In addition, also can be as conductive film covering for electromagnetic wave proof film and infrared reflection overcoat etc.Also can in electronic equipment be installed, as parts, install and use with grafting material.
< effect >
Importantly following true in the present invention: the crystallite diameter ratio of the Miller indices that obtain by X-ray diffraction (111) and (200) [crystallite diameter D
x(111)/crystallite diameter D
x(200) be] that more than 1.40 silver-colored microparticle can low-firing.And, the average grain diameter (D of this silver microparticle
sEM) be preferably 30nm above and be less than 1 μ m, can select the very average grain diameter of wide region.
The reason of silver-colored microparticle low-temperature sintering excellence of the present invention is unclear, and still, the inventor has carried out a large amount of experiments, found that: the silver-colored microparticle of the agglutinating property excellence under low temperature, crystallite diameter ratio [crystallite diameter D
x(111)/crystallite diameter D
x(200)] be more than 1.40 values.Can think that this has shown: crystallite diameter D
x(111) with crystallite diameter D
x(200) ratio is larger, and the distortion of lattice is more unstable more greatly, 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 first method 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 first method of the present invention.
The average grain diameter of silver microparticle, is used scanning electron microscope photographic means " S-4800 " (HITACHI manufacture) to take the photo of particle, uses this photo to measure particle diameter to 100 above particles, calculates its mean value, as average grain diameter (D
sEM).
The specific area of silver microparticle, with the value representation that uses " 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 and 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 of face, utilizes Scherrer formula to calculate crystallite diameter.
The Miller indices that obtain by X-ray diffraction (111) of silver microparticle and the crystallite diameter ratio of (200), used 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 being caused by heating of silver microparticle is to use silver-colored microparticle at 150 ℃ of crystallite diameter D that heat after 30 minutes
x(111) the crystallite diameter D of the silver-colored microparticle and before heating
x(111) value of, calculating according to following formula 1.In addition, heating condition is being changed into the rate of change of obtaining similarly crystallite diameter in the situation that heating 30 minutes for 210 ℃.
< formula 1 >
Crystallite diameter * 100 of the silver-colored microparticle before the crystallite diameter/heating of the silver-colored microparticle after the rate of change of crystallite diameter (%)=heating
Use the characteristic of the conductive coating of the type of the firing cream in the example of first method of the present invention, by following method, obtain., for the conductive paste of firing type described later is coated on aluminum oxide substrate, at 120 ℃ after predrying 30 minutes, at 200 ℃, 300 ℃, 400 ℃, 500 ℃, 600 ℃ of conductive films that heat 30 minutes and obtain, use 4 terminal resistance determinators " Loresta GP/MCP-T600 " (Mitsubishi Chemical of Co., Ltd. analytical technology (Mitsubishi Chemical Analytech Co., Ltd.) manufacture) measure, according to sheet resistance and thickness, calculate resistivity, transverse axis using temperature as chart, layer resistivity is drawn as the longitudinal axis, with layer resistivity, become 1 * 10
-5temperature below Ω cm represents.In addition, provided the layer resistivity of the conductive film when heating respectively 30 minutes for 120 ℃, 200 ℃ and 400 ℃.
In addition, the in the situation that of polymer-type cream, provided the conducting film that applies the conductive paste of electric conductive polymer type described later on the polyimide film at thickness 50 μ m and obtain, respectively the layer resistivity of the conductive film when heating 30 minutes for 120 ℃, 210 ℃ and 300 ℃.
The resistivity of the conductive coating in the example of first method of the present invention, for conductive paste described later is coated on polyimide film, 120 ℃ predrying after, each temperature of 150 ℃, 210 ℃ and 300 ℃ be heating and curing 30 minutes and the conductive film that obtains separately, use 4 terminal resistance determinators " Loresta GP/MCP-T600 " (Mitsubishi Chemical of Co., Ltd. analytical technology is manufactured) to measure, according to sheet resistance and thickness, calculate resistivity.
< embodiment 1-1: the manufacture > of silver-colored microparticle
To the arabo-ascorbic acid 739g(adding as reducing agent in the reaction tower of 50L, with respect to silver-colored 1mol, be 1.5mol), pure water 32.3L and ammoniacal liquor (25%) 780g(be 4.1mol with respect to silver-colored 1mol) afterwards, when being cooled to below 18 ℃, mixing, stir, prepare reducing solution.In addition, add silver nitrate 475g and pure water 6300g in the plastic containers of 20mL after, when being cooled to below 18 ℃, mixing, stir, prepare silver nitrate aqueous solution.
Then, reaction system is cooled to below 20 ℃, and in reducing solution, adds silver nitrate aqueous solution (the interpolation time is below 10 seconds) when stirring.After interpolation finishes, after stirring 30 minutes, within standing 30 minutes, make solid content precipitation.After supernatant being removed by decant, use filter paper to carry out suction strainer, then, use pure water to clean, filter, until the electrical conductivity of filtrate becomes 7 μ S/cm.
The filter cake of the silver-colored microparticle that obtains is dispersed in methanol solution again, after the moisture on silver-colored microparticle surface is replaced into methyl alcohol and filters, in vacuum drier 25 ℃ dry 6 hours.Then, to 2.4g macromolecular compound " DISPERBYK-106 " (trade name: Bi Ke chemistry Japanese Co., Ltd manufacture) is dispersed in the solution obtaining in the mixed solution (water: methyl alcohol than be 1:10) of pure water and methyl alcohol, adding the silver-colored microparticle 300g(obtaining is 0.8 % by weight with respect to silver-colored microparticle), in vacuum drier at 25 ℃ after dry 12 hours, utilize jet pulverizer to pulverize, obtain the silver-colored microparticle of embodiment 1-1.
The grain shape of the silver-colored microparticle obtaining 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 that 1.58, BET specific area value is 1.5m
2/ g, the rate of change of crystallite diameter (150 ℃ * 30 minutes) is 128%, the rate of change of crystallite diameter (210 ℃ * 30 minutes) is 179%.
< embodiment 2-1: the manufacture of conductive paste (firing type cream) >
Silver-colored microparticle 100 weight portions with respect to embodiment 1-1, add ethyl cellulose resin 2.5 weight portions, lead-less glasses material 2.5 weight portions, n-butyl phthalate 3.0 weight portions and 2, 2, 4-trimethyl-1, 3-pentanediol one isobutyl ester (TEXANOL)/1-phenoxy group-2-propyl alcohol (1:1) 15.4 weight portions, (the new base of Co., Ltd. (THINKY CORPORATION) is manufactured to use rotation-revolution mixer " Awa-tori RENTARO ARE-310 ", registration mark) carry out after premixed, use 3 rollers to carry out equably mixing, 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 ℃, after predrying 30 minutes, 200 ℃, 300 ℃, 400 ℃, 500 ℃, 600 ℃ heating 30 minutes, obtain thus conductive coating.
The layer resistivity of the conductive coating obtaining becomes 1.0 * 10
-5temperature below Ω cm is 195 ℃.In addition, the resistivity in the situation that carrying out 30 minutes heat treated for 120 ℃ is 7.7 * 10
-5Ω cm, the resistivity in the situation that carrying out 30 minutes heat treated for 200 ℃ is 9.1 * 10
-6Ω cm, the resistivity in the situation that carrying out 30 minutes heat treated for 400 ℃ is 4.7 * 10
-6Ω cm.
< embodiment 3-1: the manufacture of conductive paste (polymer-type cream) >
With respect to silver-colored microparticle 100 weight portions of embodiment 1-1, adding mylar 11.0 weight portions and curing agent 1.4 weight portions and diethylene glycol monoethyl ether makes the content of the silver-colored microparticle in conductive paste become 70wt%, carry out after premixed, use 3 rollers to carry out equably mixing, dispersion treatment, obtain the conductive paste of embodiment 3-1.
To be coated on the polyimide film of thickness 50 μ m by conductive paste obtained above (polymer-type cream), at 120 ℃, 210 ℃ and 300 ℃, heat 30 minutes respectively, obtain thus conductive coating.
Resistivity by the conductive coating obtaining in the situation that carrying out 30 minutes heat treated for 120 ℃ is 3.7 * 10
-4Ω cm, the resistivity in the situation that carrying out 30 minutes heat treated for 210 ℃ is 2.8 * 10
-6Ω cm, the resistivity in the situation that carrying out 30 minutes heat treated for 300 ℃ is 9.8 * 10
-6Ω cm.
According to above-described embodiment 1-1, embodiment 2-1 and embodiment 3-1, make silver-colored microparticle and conductive paste.Provide the silver-colored microparticle powder of respectively creating conditions and obtaining and every characteristic of conductive paste.
< embodiment 1-2～1-4 and comparative example 1-1～1-2 >
By the formation condition of silver-colored microparticle is carried out to various changes, obtain silver-colored microparticle.In addition, the particle of comparative example 1-5 is the silver particle powder of commercially available micron-scale.
Creating conditions is now shown in to table 1, every characteristic of the silver-colored microparticle obtaining is shown in to table 3.
< embodiment 1-6: the manufacture > of silver-colored microparticle
To silver nitrate 595g, the pure water 38L and ammoniacal liquor (25%) 2381g(that add as silver material in the reaction tower of 50L, with respect to silver-colored 1mol, be 10.0mol) afterwards, when being cooled to below 10 ℃, mixing, stir, prepare the silver salt complex aqueous solution.In addition, the arabo-ascorbic acid 925g(adding in the plastic containers of 20L as reducing agent is 1.5mol with respect to silver-colored 1mol) and pure water 8333g after, when being cooled to 10 ℃ below, mixing, stir, prepare the aqueous solution that contains reducing agent.
Then, reaction system is cooled to below 10 ℃, and in the silver salt complex aqueous solution, adds the aqueous solution (the interpolation time is below 10 seconds) that contains reducing agent when stirring.After interpolation finishes, after stirring 30 minutes, within standing 30 minutes, make solid content precipitation.After supernatant being removed by decant, use filter paper to carry out suction strainer, then, use pure water to clean, filter, until the electrical conductivity of filtrate becomes 20 μ S/cm.
The filter cake of the silver-colored microparticle that obtains is dispersed in methanol solution again, after the moisture on silver-colored microparticle surface is replaced into methyl alcohol and filters, in vacuum drier 25 ℃ dry 6 hours.Then, to 3.6g macromolecular compound " DISPERBYK-106 " (trade name: Bi Ke chemistry Japanese Co., Ltd manufacture) is dispersed in the solution obtaining in the mixed solution (water: methyl alcohol than be 1:10) of pure water and methyl alcohol, adding the silver-colored microparticle 300g(obtaining is 1.2 % by weight with respect to silver-colored microparticle), in vacuum drier at 25 ℃ after dry 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 the formation condition of silver-colored microparticle is carried out to various changes, obtain silver-colored microparticle.
Creating conditions is now shown in to table 2, every characteristic of the silver-colored microparticle obtaining is shown in to 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 the kind of silver-colored microparticle is carried out various changes, according to the preparation method of the conductive paste of above-described embodiment 2-1 (firing type cream), manufacture conductive paste and conductive coating.
Every characteristic of the conductive coating of creating conditions and obtaining is now shown in to 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 the kind of silver-colored microparticle is carried out various changes, according to the preparation method of the conductive paste of above-described embodiment 3-1 (polymer-type cream), manufacture conductive paste and conductive coating.
Every characteristic of the conductive coating of creating conditions and obtaining is now shown in to table 5.
[table 5]
< embodiment 4-1: the manufacture > of silver-colored microparticle
To the arabo-ascorbic acid 739g(adding as reducing agent in the reaction tower of 50L, with respect to silver-colored 1mol, be 1.5mol), pure water 33.4L and ammoniacal liquor (25%) 3808g(be 20mol with respect to silver-colored 1mol) afterwards, when being cooled to below 18 ℃, mixing, stir, prepare reducing solution.In addition, add silver nitrate 475g and pure water 1900g in the plastic containers of 20L after, when being cooled to below 18 ℃, mixing, stir, prepare silver nitrate aqueous solution.
Then, reaction system is cooled to below 20 ℃, and in reducing solution, adds silver nitrate aqueous solution (the interpolation time is below 10 seconds) when stirring.After interpolation finishes, after stirring 30 minutes, within standing 30 minutes, make solid content precipitation.After supernatant being removed by decant, use filter paper to carry out suction strainer, then, use pure water to clean, filter, until the electrical conductivity of filtrate becomes 38 μ S/cm.
The filter cake of the silver-colored microparticle that obtains is dispersed in methanol solution again, after the moisture on silver-colored microparticle surface is replaced into methyl alcohol and filters, in vacuum drier 25 ℃ dry 6 hours.Then, with respect to the silver-colored microparticle 300g obtaining, add 4.2g and be dispersed in the macromolecular compound " DISPERBYK-106 " (the Japanese Co., Ltd of trade name: Bi Ke chemistry manufactures) (being 1.4 % by weight with respect to silver-colored microparticle) in methanol solution, after carrying out stirring for 90 minutes, mixing, methyl alcohol distillation is removed.Then, in vacuum drier, after 25 ℃ are dried 6 hours, utilize jet pulverizer to pulverize, obtain the silver-colored microparticle of embodiment 4-1.
The grain shape of the silver-colored microparticle obtaining 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 that 1.62, BET specific area value is 2.9m
2/ g, the rate of change of crystallite diameter (150 ℃ * 30 minutes) is 118%, the rate of change of crystallite diameter (210 ℃ * 30 minutes) is 145%.
< embodiment 5-1: the manufacture > of conductive paste
With respect to silver-colored microparticle 100 weight portions of embodiment 4-1, adding mylar 11.0 weight portions and curing agent 1.4 weight portions and diethylene glycol monoethyl ether makes the content of the silver-colored microparticle in conductive paste become 70wt%, use rotation-revolution mixer " Awa-tori RENTARO ARE-310 " (the new base manufacture of Co., Ltd., registration mark) carry out after premixed, use 3 rollers to carry out equably mixing, dispersion treatment, obtain conductive paste.
To by conductive paste obtained above, be coated on the polyimide film of thickness 50 μ m, at 120 ℃, 210 ℃ and 300 ℃, heat 30 minutes respectively, obtain thus conductive coating.
Resistivity by the conductive coating obtaining in the situation that carrying out 30 minutes heat treated for 120 ℃ is 1.5 * 10
-5Ω cm, the resistivity in the situation that carrying out 30 minutes heat treated for 210 ℃ is 6.8 * 10
-6Ω cm, the resistivity in the situation that carrying out 30 minutes heat treated for 300 ℃ is 3.1 * 10
-6Ω cm.
According to above-described embodiment 4-1 and embodiment 5-1, make silver-colored microparticle and conductive paste.Provide the silver-colored microparticle powder of respectively creating conditions and obtaining and every characteristic of conductive paste.
< embodiment 4-2～4-5 and comparative example 4-1～4-2 >
By the formation condition of silver-colored microparticle is carried out to various changes, obtain silver-colored microparticle.
Creating conditions is now shown in to table 6, every characteristic of the silver-colored microparticle obtaining is shown in to table 9.
< embodiment 4-6: the manufacture > of silver-colored microparticle
To the silver nitrate 475g and ammoniacal liquor (25%) 3808g(that add as silver material in the reaction tower of 50L, with respect to silver-colored 1mol, be 20mol) afterwards, when being cooled to below 8 ℃, mixing, stir, prepare the silver salt complex aqueous solution.In addition, the arabo-ascorbic acid 739g(adding in the plastic containers of 20L as reducing agent is 1.5mol with respect to silver-colored 1mol) and pure water 3530g after, when being cooled to below 9 ℃, mixing, stir, prepare the aqueous solution that contains reducing agent.
Then, reaction system is cooled to below 10 ℃, and in the silver salt complex aqueous solution, adds the aqueous solution (the interpolation time is below 10 seconds) that contains reducing agent when stirring.After interpolation finishes, after stirring 30 minutes, within standing 30 minutes, make solid content precipitation.After supernatant being removed by decant, use filter paper to carry out suction strainer, then, use pure water to clean, filter, until the electrical conductivity of filtrate becomes 15 μ S/cm.
The filter cake of the silver-colored microparticle that obtains is dispersed in methanol solution again, after the moisture on silver-colored microparticle surface is replaced into methyl alcohol and filters, in vacuum drier 25 ℃ dry 6 hours.Then, with respect to the silver-colored microparticle 300g obtaining, add 4.2g and be dispersed in the macromolecular compound " DISPERBYK-106 " (the Japanese Co., Ltd of trade name: Bi Ke chemistry manufactures) (being 1.4 % by weight with respect to silver-colored microparticle) in methanol solution, after carrying out stirring for 90 minutes, mixing, methyl alcohol distillation is removed.Then, in vacuum drier, after 25 ℃ are dried 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 the formation condition of silver-colored microparticle is carried out to various changes, obtain silver-colored microparticle.
Creating conditions is now shown in to table 7, every characteristic of the silver-colored microparticle obtaining is shown in to 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, carry out adding n-butylamine 151.6g in cooling with water-bath after, when being cooled to below 18 ℃, mixing, stir, preparation A liquid.In addition, measure arabo-ascorbic acid 248.8g in the beaker of 5L, interpolation 1600mL water adds methyl alcohol 800mL after stirring and making its dissolving, mixes, stirs, preparation B liquid when being cooled to below 18 ℃.
Then, B liquid is stirred, when reaction system being cooled to below 20 ℃, with 1 hour 20 minutes, A drop is added in B liquid.After dropping finishes, after stirring 14 hours, within standing 30 minutes, make solid content precipitation.After supernatant being removed by decant, use filter paper to carry out suction strainer, then, use methyl alcohol and pure water to clean, filter.
By the solid content of the silver-colored microparticle obtaining in vacuum drier after 30 minutes dry 6 hours, with respect to the silver-colored microparticle 24g obtaining, add 0.48g and be dispersed in the macromolecular compound " DISPERBYK-106 " (the Japanese Co., Ltd of trade name: Bi Ke chemistry manufactures) (being 2.0 % by weight with respect to silver-colored microparticle) in methanol solution, after carrying out stirring for 90 minutes, mixing, methyl alcohol distillation is removed.Then, in vacuum drier, after 25 ℃ are dried 6 hours, utilize jet pulverizer to pulverize, obtain the silver-colored microparticle of embodiment 4-10.
Creating conditions is now shown in to table 8, every characteristic of the silver-colored microparticle obtaining is shown in to table 9.
< embodiment 4-11～4-13 and comparative example 4-5～4-6 >
By the formation condition of silver-colored microparticle is carried out to various changes, obtain silver-colored microparticle.
Creating conditions is now shown in to table 7, every characteristic of the silver-colored microparticle obtaining is shown in to table 9.
[table 9]
The manufacture > of < conductive coating paint
< embodiment 5-2～5-13 and comparative example 5-1～5-7 >
Except the kind of silver-colored microparticle is carried out various changes, according to the preparation method of the conductive coating paint of above-described embodiment 5-1, manufacture conductive coating paint and conductive film.
Every characteristic of the conductive coating of creating conditions and obtaining is now shown in to table 10.
[table 10]
Utilizability in industry
Silver-colored microparticle of the present invention, the crystallite diameter ratio of the Miller indices that obtain by X-ray diffraction (111) and (200) [crystallite diameter D
x(111)/crystallite diameter D
x(200) be] more than 1.40, therefore, be suitable as the raw material of conductive paste etc. that can low-firing.
Claims (12)
1. a silver-colored microparticle, is characterized in that:
The crystallite diameter ratio of the Miller indices that obtain by X-ray diffraction (111) and (200) [crystallite diameter D
x(111)/crystallite diameter D
x(200) be] more than 1.40.
2. silver-colored microparticle as claimed in claim 1, is characterized in that:
Average grain diameter (D
sEM) for 100nm is above and be less than 1 μ m.
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. the silver-colored microparticle as described in any one in claim 1～3, is characterized in that:
The crystallite diameter D of Miller indices (200)
x(200) be below 14nm.
5. the silver-colored microparticle as described in any one in claim 1～4, is characterized in that:
The particle surface of silver microparticle is by one kind or two or more being coated being selected from the more than 1000 high score subclass dispersant of number-average molecular weight.
6. silver-colored microparticle as claimed in claim 1, is characterized in that:
Average grain diameter (D
sEM) for 30nm is above and be less than 100nm.
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 any one in claim 1,6 and 7, 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 any one in claim 1 and 6～8, is characterized in that:
By molecular weight, more than 10000 macromolecular compounds is coated the particle surface of silver microparticle.
10. a conductive paste, is characterized in that:
Contain the silver-colored microparticle described in any one in claim 1～9.
11. 1 kinds of conductive films, is characterized in that:
Right to use requires the conductive paste described in 10 to form.
12. 1 kinds of electronic devices, is characterized in that:
There is the conductive film described in claim 11.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| 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 | ||
| 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 |
| 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 true CN103702786A (en) | 2014-04-02 |
| CN103702786B CN103702786B (en) | 2015-07-29 |
Family
ID=47629170
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| 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) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107614160A (en) * | 2015-06-05 | 2018-01-19 | 同和电子科技有限公司 | Silver particles dispersion liquid |
| CN108650873A (en) * | 2018-05-15 | 2018-10-12 | 河南科技大学第附属医院 | A kind of environmental protecting device eliminated nuclear magnetic resonance and human body radiation is endangered |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3115130A4 (en) | 2014-03-05 | 2017-10-25 | Sekisui Chemical Co., Ltd. | Conductive filler, method for manufacturing conductive filler, and conductive paste |
| 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 |
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| 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 |
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| 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 KR KR1020147001483A patent/KR20140047663A/en not_active Application Discontinuation
- 2012-07-26 CN CN201280036601.7A patent/CN103702786B/en not_active Expired - Fee Related
- 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 |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107614160A (en) * | 2015-06-05 | 2018-01-19 | 同和电子科技有限公司 | Silver particles dispersion liquid |
| CN108650873A (en) * | 2018-05-15 | 2018-10-12 | 河南科技大学第附属医院 | A kind of environmental protecting device eliminated nuclear magnetic resonance and human body radiation is endangered |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103702786B (en) | 2015-07-29 |
| WO2013018645A1 (en) | 2013-02-07 |
| KR20140047663A (en) | 2014-04-22 |
| TW201315685A (en) | 2013-04-16 |
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