CN104010752A - Silver fine particles, production process therefor, conductive paste, conductive membrane and electronic device, containing said silver fine particles - Google Patents
Silver fine particles, production process therefor, conductive paste, conductive membrane and electronic device, containing said silver fine particles Download PDFInfo
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- CN104010752A CN104010752A CN201280062600.XA CN201280062600A CN104010752A CN 104010752 A CN104010752 A CN 104010752A CN 201280062600 A CN201280062600 A CN 201280062600A CN 104010752 A CN104010752 A CN 104010752A
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- silver
- colored particulate
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- fine particles
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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
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
-
- 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
-
- 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
- B22F1/056—Submicron particles having a size above 100 nm up to 300 nm
-
- 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
- B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
- B22F1/102—Metallic powder coated with organic material
-
- 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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- 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
-
- 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
- B22F2301/00—Metallic composition of the powder or its coating
- B22F2301/25—Noble metals, i.e. Ag Au, Ir, Os, Pd, Pt, Rh, Ru
- B22F2301/255—Silver or gold
-
- 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
- B22F2304/00—Physical aspects of the powder
- B22F2304/05—Submicron size particles
- B22F2304/054—Particle size between 1 and 100 nm
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
Abstract
The present invention pertains to: silver fine particles with excellent low-temperature sinterability; a production process therefor; and a conductive paste, a conductive membrane and an electronic device, containing the silver fine particles. In a process for producing silver fine particles which comprises preparing an alcoholic solution (A) of a silver nitrate-amine complex prepared using silver nitrate and at least one water-soluble C2-4 aliphatic amine, preparing, separately from the solution (A), an aqueous solution (B) in which either ascorbic acid or erythorbic acid and a halide are dissolved, adding a mixture of the solution (A) with the solution (B) into a vessel in which water has been put, stirring the resulting mixture, and then subjecting the thus obtained silver fine particles to washing and drying, at least 1.6*10<-3> mol of a halide per mol of silver nitrate is added to the solution (B), whereby an aggregate silver fine particle slurry can be obtained to facilitate the subsequent washing. Thus, silver fine particles which have a carbon content of 0.25wt% or less and thus exhibit excellent low-temperature sinterability can be obtained.
Description
Technical field
The silver-colored particulate that the average grain diameter that the present invention relates to low-temperature sintering excellence is 30～120nm and manufacture method thereof and the conductive paste that contains this silver particulate, conductive film and electronic device.
Background technology
The electrode of electronic device or the formation of circuit pattern, the conductive paste that contains metallic particles by use prints electrode or circuit pattern on substrate, heats afterwards to fire metallic particles sintering contained in conductive paste is carried out.In recent years, there is the trend of low temperature in this heating firing temperature.
For example, as the installation base plate of electronic device, generally speaking, in order to be heated to 300 DEG C of left and right, excellent heat resistance, use polyimides flexible base, board processed, but due to expensive, recently, instead PET (PETG) substrate and PEN (PEN) substrate more at a low price in investigation of materials.But pet substrate is compared with PEN substrate and polyimides flexible base, board processed, heat resistance is low, need to heat and fire below at 150 DEG C especially for the PET film substrate of film wiring plate.
In addition, as long as can heat and fire lower than the temperature of 200 DEG C, on the substrate such as Merlon or paper, form electrode or circuit pattern and also become possibility, can expect the purposes expansion of various electrode materials etc.
As the metallic particles of the raw material of the such conductive paste that can realize low-firing, can expect nano level silver-colored particulate.Reason is that while being nanoscale due to the size of metallic particles, surface-active is high, and fusing point significantly reduces compared with metal derby, therefore, can carry out sintering with low temperature.In addition, compared with other conductive particle such as copper, although that silver-colored particulate exists is expensive, the shortcoming that easily causes migration in metallic particles, compared with thering is the copper of equal extent resistivity, not oxidizable, therefore easily operation.
In addition, nano level silver-colored particulate can be in low-temperature sintering, and, once sintering maintains heat resistance, utilizing the not available character of these existing scolders, can expect to replace material as unleaded scolder.
At present as stability and high efficiency manufacture the method for the fine silver-colored particle of excellent dispersion, the silver powder that contains halogen that shrinkage factor when the curing heating-up temperature that proposed under the existence of halide ion, the method for silver ion reduction (patent documentation 1), resin type to be stuck with paste is high and simply and at an easy rate obtain the manufacture method (patent documentation 2) of this silver powder that contains halogen.In addition, as for making sintering under low temperature (600 DEG C of front and back) carry out, manufacture the metal dust of the sintered component of excellent ductility, the halogen that 5～2000ppm is contained on the known surface at metal dust or halide (patent documentation 3).
In addition, by being controlled at below 30 DEG C from being reacted to dry whole operations, as the raw material that can realize conductive paste of low-firing etc., the silver-colored particle (patent documentation 4) of the polycrystallization that known average grain diameter is 30～100nm.
Prior art document
Patent documentation
Patent documentation 1: TOHKEMY 2008-274423 communique
Patent documentation 2: TOHKEMY 2010-77493 communique
Patent documentation 3: TOHKEMY 2005-325411 communique
Patent documentation 4: TOHKEMY 2011-80094 communique
Summary of the invention
Invent problem to be solved
In above-mentioned patent documentation 1, disclose under the existence of halide ion the method for silver ion reduction, but in the manufacture method of recording at patent documentation 1, shown in comparative example, because halid addition is few, the silver-colored particulate of generation forms dispersion as described later, follow-up is clean insufficient, therefore, the carbon amount that can not make the silver-colored particulate obtaining is below 0.25 % by weight, is difficult to obtain the silver-colored particulate of low-temperature sintering excellence.
In addition, in patent documentation 2, the silver powder that contains halogen is disclosed, but, owing to adding halid period after silver-colored reduction reaction, and form silver chlorate when the reduction reaction and make compared with its thawless situation, contained halogen easily departs from or ionization, particularly, as being used for electrode of the present invention or the conductive paste of formation of circuit pattern and the silver-colored particulate that the purposes of conductive film is used, halogen is attached to particle surface with Ionized state simply, so not preferred.
In patent documentation 3, the halogen or the halide that contain 5～2000ppm on the surface of metal dust are disclosed, but, the metal dust of recording in patent documentation 3 is that metal dust extrusion forming is made to powder compact, use with 500～900 DEG C of sintering, the adding purpose of halogen is to reduce ductility and the dimensional contraction of sintered component, therefore, with above-mentioned same, particularly as being used for electrode of the present invention or the conductive paste of formation of circuit pattern and the silver-colored particulate that the purposes of conductive film is used, halogen is attached to particle surface with Ionized state simply, so it is not preferred.
In patent documentation 4, the silver-colored particle of the polycrystallization that is 30～100nm as the average grain diameter of raw material that can realize conductive paste of low-firing etc. is disclosed by being controlled at below 30 DEG C from being reacted to dry whole operations.But shown in comparative example, owing to not adding halide, thereby the silver-colored particulate generating forms dispersion as described later, follow-up is clean insufficient, therefore, the carbon amount that can not make obtained silver-colored particulate is below 0.25 % by weight, is difficult to obtain the silver-colored particulate of low-temperature sintering excellence.And baking temperature also needs to be controlled at below 30 DEG C, therefore, industrial unfavorable.
Therefore, technical task of the present invention is to provide the silver-colored particulate that a kind of average grain diameter of low-temperature sintering excellence is 30～120nm and manufactures efficiently the method for this silver particulate.
For solving the means of problem
Above-mentioned technical task can be realized by the present invention as described below.
, the invention provides a kind of manufacture method of silver-colored particulate, it is characterized in that: the aliphatic amine that the carbon number that uses silver nitrate and more than one water-soluble or water dissolvable is 2～4, prepare the alcoholic solution (A liquid) of the amine complex of silver nitrate, prepare respectively and be dissolved with ascorbic acid or arabo-ascorbic acid and the halid aqueous solution (B liquid) with above-mentioned A liquid, use silent oscillation mixer that above-mentioned A liquid and above-mentioned B liquid are mixed, the mixture obtaining is added in the container that water is housed, stir, afterwards, obtained silver-colored particulate is cleaned, dry, wherein, in above-mentioned B liquid, add 1.6 × 10 with respect to 1 equimolar silver nitrate
-3halide (the present invention 1) more than mole.
In addition, the invention provides a kind of silver-colored particulate being obtained by the method described in the present invention 1, it is characterized in that: the carbon amount of silver-colored particulate is 0.25 % by weight following (the present invention 2).
In addition, the silver-colored particulate as described in the present invention 2, the particle surface of silver-colored particulate is more than 10000 macromolecular compound coated (the present invention 3) by molecular weight.
In addition, the silver-colored particulate as described in the present invention 2 or the present invention 3, average grain diameter (D
sEM) be the above 120nm of 30nm following (the present invention 4).
In addition, the invention provides the conductive paste (the present invention 5) of the silver-colored particulate described in any one in a kind of the present invention of containing 2～the present invention 4.
In addition, the invention provides the conductive film (the present invention 6) that the conductive paste described in a kind of the present invention of use 5 forms.
In addition, the invention provides the electronic device (the present invention 7) of the conductive film described in a kind of the present invention of having 6.
Invention effect
The carbon content of silver-colored particulate of the present invention after due to reduction reaction is low, is suitable as the raw material that can realize conductive paste of low-firing etc.
In addition, the manufacture method of silver-colored particulate of the present invention, can reduce the carbon content of the silver-colored particulate after reduction reaction, and can obtain silver-colored particulate with high yield, therefore, is suitable as the manufacture method of the silver-colored particulate of low-temperature sintering excellence.
Detailed description of the invention
The present invention will be described in further detail below.
First, the manufacture method of silver-colored particulate of the present invention is described.
Silver-colored particulate of the present invention obtains by the following method: the alcoholic solution (A liquid) of the amine complex of the silver nitrate that the aliphatic amine that the carbon number of preparation use silver nitrate and more than one water-soluble or water dissolvable is 2～4 makes, prepare respectively and be dissolved with ascorbic acid or arabo-ascorbic acid and the halid aqueous solution (B liquid) with above-mentioned A liquid, use silent oscillation mixer that above-mentioned A liquid and above-mentioned B liquid are mixed, the mixture obtaining is added in the container that water is housed, stir, afterwards, obtained silver-colored particulate is cleaned, is dried.
The aliphatic amine that the alcoholic solution (A liquid) of the amine complex of silver nitrate of the present invention can be 2～4 by the silver of mixed nitrate in alcoholic solution and more than one carbon numbers water-soluble or water dissolvable obtains.The addition of aliphatic amine is preferably 2.0～2.5 moles with respect to 1 equimolar silver nitrate, more preferably 2.0～2.3 moles.When the amount of aliphatic amine during lower than 2.0 moles, exists the trend that easily generates large particle with respect to 1 mole of silver nitrate.
The aliphatic amine that is 2～4 as carbon number of the present invention, importantly use the material of water-soluble or water dissolvable, particularly, can use ethamine, n-propylamine, isopropylamine, n-butylamine, isobutyl amine etc., consider low-temperature sintering and the operability of silver-colored particulate, preferably n-propylamine and n-butylamine.
As alcohol of the present invention, can use alcohol having a miscibility with water.Particularly, can use methyl alcohol, ethanol, propyl alcohol and isopropyl alcohol etc., particular methanol and ethanol.These alcohol can use separately also can mix use.
In the present invention, prepare respectively and be dissolved with ascorbic acid or arabo-ascorbic acid and the halid aqueous solution (B liquid) with above-mentioned A liquid.The addition of ascorbic acid or arabo-ascorbic acid is preferably 1.0～2.0 moles with respect to 1 mole of the silver nitrate in the A liquid mixing, more preferably 1.0～1.8 moles.In the time that ascorbic acid or arabo-ascorbic acid exceed 2.0 moles with respect to 1 mole of silver nitrate, there is the silver-colored particulate trend of aggegation each other generating, so not preferred.
As halide of the present invention, can use and be selected from potassium chloride (KCl), sodium chloride (NaCl), ammonium chloride (NH
4cl), KBr (KBr), sodium bromide (NaBr), ammonium bromide (NH
4br), KI (KI), sodium iodide (NaI) and ammonium iodide (NH
4i) one or more in.The chlorides such as preferred potassium chloride (KCl), sodium chloride (NaCl).
As halid addition, with respect to 1 mole of the silver nitrate in the A liquid mixing, halide is preferably 1.6 × 10
-3～8.0 × 10
-3mole, more preferably 1.7 × 10
-3～6.0 × 10
-3mole, more preferably 1.8 × 10
-3～4.0 × 10
-3mole.When halid addition exceedes 8.0 × 10 with respect to 1 mole of silver nitrate
-3mole time, the effect that the slurry that makes silver-colored particulate obtaining by interpolation halide forms state of aggregation is saturated, and when halide exists above with requirement, the silver-colored particulate using as the conductive paste of the formation for electrode or circuit pattern and the purposes of conductive film is not preferred.In addition, when halid addition with respect to 1 mole of silver nitrate lower than 1.6 × 10
-3mole time, because halid amount is very few, the slurry of the silver-colored particulate obtaining is in dispersity, follow-up cleanly becomes insufficient, therefore, being difficult to make the carbon amount of silver-colored particulate is below 0.25 % by weight.
The alcoholic solution (A liquid) of the amine complex of silver nitrate and be dissolved with ascorbic acid or arabo-ascorbic acid and the halid aqueous solution (B liquid), uses silent oscillation mixer to mix, and adds in the container that water is housed and stirs.With in the alcoholic solution (A liquid) of the amine complex of silver nitrate, drip the method that is dissolved with the method for ascorbic acid or arabo-ascorbic acid and the halid aqueous solution (B liquid) or is being dissolved with the alcoholic solution (A liquid) of the amine complex of dropping silver nitrate in arabo-ascorbic acid and the halid aqueous solution (B liquid) and compare, the initial stage generation A liquid of reduction reaction and the melting concn of B liquid are certain, therefore, easily obtain the more uniform product of size distribution of obtained silver-colored particulate.
Use silent oscillation mixer by the alcoholic solution of the amine complex of silver nitrate (A liquid) be dissolved with ascorbic acid or arabo-ascorbic acid and the halid aqueous solution (B liquid) and mix, obtained reaction solution is added in the container that water is housed, silver concentration is adjusted to the scope of 0.1～1.0mol/L, carry out more than 30 minutes stirring, afterwards, according to conventional method, use alcohol and water that obtained silver-colored particulate is filtered, washed.Now, clean until the electrical conductivity of filtrate reaches below 60 μ S/cm.
The above-mentioned filter cake of cleaning the silver-colored particulate obtaining is disperseed in hydrophilic organic solvent again, after the moisture of silver-colored microparticle surfaces is replaced as to hydrophilic organic solvent, according to conventional method, the silver-colored particulate that filtration is obtained in temperature below 40 DEG C, preferably 30 DEG C be dried below, or after vacuum drying, pulverize according to conventional method, thus, can obtain silver-colored particulate of the present invention.By the moisture of silver-colored microparticle surfaces is replaced as to hydrophilic organic solvent, can prevent from forming the dried silver-colored particulate state of firm aggegation each other, pulverization process after this or surface treatment pulverization process etc. becomes easy.
As hydrophilic organic solvent, can use alcohol and the acetone etc. such as methyl alcohol, ethanol, propyl alcohol.While considering to pass through to be dried except desolventizing, particular methanol and ethanol.
Silver-colored particulate of the present invention preferably utilizes more than 10000 macromolecular compound of molecular weight to carry out surface treatment before pulverization process.The covering amount of more than 10000 macromolecular compound of molecular weight, is preferably 0.2～4 % by weight with respect to silver-colored particulate, more preferably 0.3～3 % by weight.Be above-mentioned scope by making the treating capacity of macromolecular compound, can obtain sufficient treatment effect by pulverization process.By utilizing macromolecular compound to carry out surface treatment, in the pulverization process of carrying out afterwards, can obtain high pulverization process effect, can carry out more uniform pulverization process.On the other hand, add macromolecular compound in the reduction evolution reaction of silver-colored particulate time, aspect the uniformity for the treatment of capacity and treatment effect, existing problems, produce aggegation piece in the pulverization process of carrying out afterwards, the dispersiveness of the silver-colored particulate obtaining in electroconductive paste becomes difficulty, so not preferred.
Utilize the surface treatment of the silver-colored particulate of macromolecular compound to carry out as follows: hydrophilic organic solvent is replaced by utilizing, dried silver-colored particulate is scattered in the macromolecular compound solution that is dissolved with macromolecular compound in organic solvent again, after slowly stirring 30～300 minutes, remove organic solvent, be dried.
The pulverizing that utilizes macromolecular compound to carry out surface-treated silver particulate is preferably used jet pulverizer.
Then, silver-colored particulate of the present invention is described.
Silver-colored particulate of the present invention is the silver-colored particulate making by above-mentioned manufacture method, it is characterized in that: the carbon amount of the silver-colored particulate slurry after reduction reaction being cleaned, is dried to the silver-colored particulate obtaining is 0.25 % by weight.
In the time that the carbon amount of the silver-colored particulate slurry after reduction reaction being cleaned, is dried the silver-colored particulate obtaining exceedes 0.25 % by weight, low-temperature sintering suffers damage, so not preferred.In addition, lower limit is generally 0.15 % by weight, when lower than this lower limit, has the wetability downward trend to solvent and resin.More preferably 0.15～0.24 % by weight, more preferably 0.16～0.23 % by weight.
Average grain diameter (the D of silver-colored particulate of the present invention
sEM) be preferably below the above 120nm of 30nm, more preferably below the above 110nm of 35nm, more preferably below the above 100nm of 40nm.By making average grain diameter (D
sEM) in above-mentioned scope, use the miniaturization of its electronic device obtaining to become easy.As average grain diameter (D
sEM) during lower than 30nm, the surface-active that silver-colored particulate has is high, in order stably to maintain this trickle particle diameter, need to adhere to a large amount of organic matter etc., so not preferred.
Crystallite diameter (the D of silver-colored particulate of the present invention
x) be preferably below 30nm more preferably 10～29nm, more preferably 10～28nm.As crystallite diameter (D
x) while exceeding 30nm, the reactivity in silver-colored particulate reduces, low-temperature sintering suffers damage, so not preferred.In addition, as crystallite diameter (D
x) during lower than 10nm, silver-colored particulate becomes unstable, also start at normal temperatures to partially sinter, melting, so not preferred.
Polycrystallization degree [average grain diameter (the D of silver-colored particulate of the present invention
sEM) and crystallite diameter (D
x) ratio (D
sEM/ D
x)] be more than 2.8, be preferably more than 3.0, more preferably more than 3.2.When polycrystallization degree is lower than 2.8 time, because increasing, the crystallite diameter in silver-colored particulate approaches monocrystalline, and therefore, the reactivity in silver-colored particulate reduces, and low-temperature sintering suffers damage, so not preferred.The higher limit of above-mentioned polycrystallization degree is 10 left and right, is preferably 8 left and right.
The low-temperature sintering of silver-colored particulate of the present invention is by the crystallite diameter (D causing due to heating described later
x) the rate of change [(crystallite diameter (D of the silver-colored particulate 150 DEG C of heating after 30 minutes
xcrystallite diameter (the D of the silver-colored particulate before)/heating
x)) × 100] evaluate the crystallite diameter (D preferably causing due to the heating of 150 DEG C
x) rate of change be more than 130%, more preferably more than 135%.As crystallite diameter (D
x) rate of change lower than 130% time, low-temperature sintering excellence hardly.In the present invention, in 210 DEG C of heating situation of 30 minutes, preferably crystallite diameter (D
x) rate of change be more than 140%, more preferably more than 150%.
The BET specific area value of silver-colored particulate of the present invention is preferably 10m
2below/g, more preferably 8m
2below/g.When BET specific area value exceedes 10m
2when/g, use the viscosity of its conductive paste obtaining to uprise, so not preferred.
The content of halogen of silver-colored particulate of the present invention, with respect to 1 mole of silver, preferably halogen is 1.6 × 10
-3～8.0 × 10
-3mole, more preferably 1.7 × 10
-3～6.0 × 10
-3mole, more preferably 1.8 × 10
-3～4.0 × 10
-3mole.When the content of halogen exceedes 8.0 × 10 with respect to 1 mole of silver
-3mole time, content of halogen is too much, the silver-colored particulate using as the conductive paste of the formation for electrode or circuit pattern and the purposes of conductive film is not preferred.
The grain shape of silver-colored particulate of the present invention is preferably spherical or granular.
Silver-colored particulate of the present invention is preferably cleaned the silver-colored particulate slurry after above-mentioned reduction reaction, by molecular weight, more than 10000 macromolecular compounds is coated the particle surface of the dry silver-colored particulate obtaining.When molecular weight is lower than 10000 time, in the pulverization process of carrying out afterwards, produce aggegation piece, the dispersiveness of the silver-colored particulate obtaining in conductive paste becomes difficulty, so not preferred.In addition, be limited to 100000 left and right on the molecular weight of macromolecular compound, when molecular weight is during higher than this higher limit, viscosity increased, becomes difficulty to the uniform treatment of silver-colored microparticle surfaces.Consider that macromolecular compound is at uniformity and the treatment effect of the processing of silver-colored microparticle surfaces, preferably use simultaneously and there is the dispersant of acidic functionality and basic functionality Liang Zhong functional group or there is the dispersant of acid number and there is the dispersant of amine value.
As above-mentioned macromolecular dispersant, can use the dispersant of generally selling as pigment dispersing agent, particularly, can enumerate ANTI-TERRA-U, ANTI-TERRA-205, DISPERBYK-101, DISPERBYK-102, DISPERBYK-106, DISPERBYK-108, DISPERBYK-109, DISPERBYK-110, DISPERBYK-111, DISPERBYK-112, DISPERBYK-116, DISPERBYK-130, DISPERBYK-140, DISPERBYK-142, DISPERBYK-145, DISPERBYK-161, DISPERBYK-162, DISPERBYK-163, DISPERBYK-164, DISPERBYK-166, DISPERBYK-167, DISPERBYK-168, DISPERBYK-170, DISPERBYK-171, DISPERBYK-174, DISPERBYK-180, DISPERBYK-182, DISPERBYK-183, DISPERBYK-184, DISPERBYK-185, DISPERBYK-2000, DISPERBYK-2001, DISPERBYK-2008, DISPERBYK-2009, DISPERBYK-2022, DISPERBYK-2025, DISPERBYK-2050, DISPERBYK-2070, DISPERBYK-2096, DISPERBYK-2150, DISPERBYK-2155, DISPERBYK-2163, DISPERBYK-2164, BYK-P104, BYK-P104S, BYK-P105, BYK-9076, BYK-9077, BYK-220S, (production of BYK Japan Co., Ltd.), EFKA4008, EFKA4009, EFKA4046, EFKA4047, EFKA4010, EFKA4015, EFKA4020, EFKA4050, EFKA4055, EFKA4060, EFKA4080, EFKA4300, EFKA4330, EFKA4400, EFKA4401, EFKA4402, EFKA4403, EFKA4406, EFKA4800, EFKA5010, EFKA5044, EFKA5244, EFKA5054, EFKA5055, EFKA5063, EFKA5064, EFKA5065, EFKA5066, EFKA5070 (production of BASF JAPAN Co., Ltd.), SOLSPERSE3000, SOLSPERSE13240, SOLSPERSE13940, SOLSPERSE16000, SOLSPERSE17000, SOLSPERSE18000, SOLSPERSE20000, SOLSPERSE21000, SOLSPERSE24000SC, SOLSPERSE24000GR, SOLSPERSE26000, SOLSPERSE27000, SOLSPERSE28000, SOLSPERSE31845, SOLSPERSE32000, SOLSPERSE32500, SOLSPERSE32550, SOLSPERSE34750, SOLSPERSE35100, SOLSPERSE35200, SOLSPERSE36000, SOLSPERSE36600, SOLSPERSE37500, SOLSPERSE38500, SOLSPERSE39000, SOLSPERSE41000 (Japanese Lubrizol Co., Ltd. produce), Ajisper PB821, Ajisper PB822, Ajisper PB881, Ajisper PN-411, Ajisper PA-111, (production of Ajinomoto Fine-Techno Co., Ltd.), DISPARLON KS-860, DISPARLON KS-873N, DISPARLON7004, DISPARLON1831, DISPARLON1850, DISPARLON1860, DISPARLON DA-7301, DISPARLON DA-325, DISPARLON DA-375, DISPARLON DA-234 (nanmu originally changes into Co., Ltd. and produces), Flowlen DOPA-15B, Flowlen DOPA-17HF, Flowlen DOPA-22, Flowlen DOPA-33, Flowlen G-700, Flowlen G-820, Flowlen G-900 (Kyoeisha Chemical Co., Ltd.'s production) etc.These pigment dispersing agents can use one or combine two or more uses.
Then, the conductive paste that contains silver-colored particulate of the present invention is described.
Conductive paste of the present invention can be for firing any form that type is stuck with paste and polymer-type is stuck with paste, and for firing type when paste, comprises silver-colored particulate of the present invention and frit, can coordinate as required other composition such as adhesive resin, solvent.In addition, in the time sticking with paste for polymer-type, comprise silver-colored particulate of the present invention and solvent, can coordinate as required other compositions such as adhesive resin, curing agent, dispersant, fluidity regulator.
As adhesive resin, can use the known adhesive resin in this field, for example, can enumerate the various modified polyester resins such as the cellulose-based resin such as ethyl cellulose, nitrocellulose, mylar, urethane modified polyester resin, epoxy modified polyester resin, acrylic acid modified polyester, polyurethane resin, trichloroactic acid ethylene copolymer, acrylic resin, epoxy resin, phenolic resins, alkyd resins, butyral resin, polyvinyl alcohol, polyimides, polyamidoimide etc.These adhesive resins can use separately also can be also with two or more.
As solvent, can use solvent well known in the art, for example, can enumerate the hydrocarbon system solvents such as tetradecane, toluene, dimethylbenzene, ethylbenzene, diethylbenzene, isopropylbenzene, penta benzene, cymene, tetrahydronaphthalene and petroleum aromatic hydrocarbon mixture; Ether or the glycol ethers series solvent of 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 mono-n-butyl Ether, Tripropylene glycol monomethyl Ether etc.; The diol ester series solvent of ethylene glycol monomethyl ether acetate, ethylene glycol monoethylether acetate, ethylene glycol monomethyl ether acetate, propylene glycol methyl ether acetate, propylene glycol monoethyl ether acetate etc.; The ketone series solvent of methylisobutylketone, cyclohexanone etc.; The terpenol of terpineol, linalool, geraniol, citronellol etc.; The alcohol series solvent of n-butanol, sec-butyl alcohol, the tert-butyl alcohol etc.; The glycol series solvent of ethylene glycol, diethylene glycol etc.; Gamma-butyrolacton and water etc.Solvent can use separately also can be also with two or more.
The content of the silver-colored particulate in conductive paste according to purposes and different, for example, in the time being used to form the purposes of wiring etc., preferably approaches 100 % by weight as far as possible.
Conductive paste of the present invention can be beaten burst various mixing rolls, the dispersion machines such as mixer, jar mill, three-roll grinder, rotary mixer, double shaft mixer by use makes each composition mix, disperse to obtain.
Conductive paste of the present invention can be applicable to the various coating processes such as serigraphy, ink-jet method, intaglio printing, hectographic printing, roller coat, flow coat, spraying, spin coating, dip-coating, blade coating, plating.
In addition, the electrode that conductive paste of the present invention can be used as FPD (flat-panel monitor), solar cell, organic EL etc. forms or LSI substrate wiring forms and the wiring of the landfill of fine ditch, perforation, contact hole etc. forms material.In addition, certainly the internal electrode that is also suitable for multi-layer ceramic capacitor or laminated inductance coil forms the purposes of firing under the high temperature of using etc., owing to can realizing low-firing, the wiring being suitable as on flexible base, board or IC-card, other substrate forms material and electrode formation material.In addition, also can be used in electromagnetic shielding film or infrared reflection shielding etc. as conductive cell envelope.In installing, electronic equipment also can use with grafting material as parts installation.
< effect >
Key point of the present invention is the fact of the low-temperature sintering excellence of silver-colored particulate of the present invention, silver-colored particulate of the present invention makes by following method: the alcoholic solution (A liquid) of the amine complex of the silver nitrate that the aliphatic amine that the carbon number of preparation use silver nitrate and more than one water-soluble or water dissolvable is 2～4 makes, prepare respectively and be dissolved with ascorbic acid or arabo-ascorbic acid and the halid aqueous solution (B liquid) with above-mentioned A liquid, use silent oscillation mixer that above-mentioned A liquid and above-mentioned B liquid are mixed, the mixture obtaining is added in the container that water is housed, stir, afterwards, obtained silver-colored particulate is cleaned, dry.
About the reason of the low-temperature sintering excellence of the silver-colored particulate of the present invention obtaining by above-mentioned manufacture method, the present inventor thinks: by adding 1.6 × 10 with respect to 1 mole of silver nitrate in the solution of reduction reaction
-3mole halide, the slurry of the silver-colored particulate obtaining forms aggegation system, clean becoming easily afterwards, therefore can make the carbon amount of silver-colored particulate below 0.25 % by weight.In addition, according to above-mentioned manufacture method, even in the situation that baking temperature exceedes 30 DEG C, it is more than 2.8 polycrystallinities that the silver-colored particulate obtaining also has polycrystallization degree.
Embodiment
, illustrate embodiments of the invention below, illustrate the present invention.
The average grain diameter of silver particulate, use scanning electron microscope photo " S-4800 " (HITACHI production), take the photo of particle, use this photo to measure to 100 above particles the particle diameter that is equivalent to ball, calculate its mean value, as average grain diameter (D
sEM).
The value representation of the specific area of silver particulate to use " Monosorb MS-11 " (production of Quanta Chrome Co., Ltd.) to record by BET method.
Silver-colored particulate slurry after reduction reaction is cleaned, is dried to the carbon amount of the silver-colored particulate obtaining, use " a metal analysis of carbon and sulfur device EMIA-2200 type rises abruptly " (Horiba Seisakusho K.k.'s production) to try to achieve.
Crystallite diameter (the D of silver particulate
x), use X-ray diffraction device " RINT2500 " (Rigaku of Co., Ltd. production), use the K alpha ray of Cu as radiographic source, obtain the half-peak breadth at the peak of facial index (1,1,1) face, calculate crystallite diameter by Scherrer formula.
The polycrystallization degree of silver particulate, with average grain diameter (D
sEM) and crystallite diameter (D
x) ratio (D
sEM/ D
x) represent.
The content of halogen of silver in particulate obtained by the combustion tube type oxygen burning/chromatography of ions, in this mensuration, by test sample 20mg in combustion tube with 1100 DEG C of burnings, collect the gas of generation, utilize ion chromatography.
The rate of change (%) of the crystallite diameter causing due to heating of silver particulate is the value of obtaining by following method: use by silver-colored particulate 150 DEG C of heating the crystallite diameter (D after 30 minutes
x) and heating before the crystallite diameter (D of silver-colored particulate
x), calculate according to following mathematical expression 1.Wherein, in the time heating condition being changed into 210 DEG C, 30 minutes, obtain similarly the rate of change of crystallite diameter.
< mathematical expression 1 >
Crystallite diameter (the D of the silver-colored particulate after rate of change (the %)=heating of crystallite diameter
xcrystallite diameter (the D of the silver-colored particulate before)/heating
x) × 100
The resistivity of conductive coating, on polyimide film, be coated with conductive paste described later, after dry with 120 DEG C of preparations, be heating and curing at each temperature 30 minutes at 150 DEG C, 210 DEG C and 300 DEG C, use respectively 4 terminal resistance determinators " Loresta-GP MCP-T600 " (Mitsubishi Chemical Analytech production) to measure to the conductive film obtaining thus, calculate resistivity by sheet resistance and thickness.
< embodiment 1-1: the manufacture > of silver-colored particulate
Add nitre acid Silver 5.16kg, methyl alcohol 25.8L and n-butylamine 4.89kg in the container of 50L after, limit is cooled to 15 DEG C with following mix and blend, preparation A liquid.In addition, measure water 27.8L and arabo-ascorbic acid 8.03kg in the container of 50L, after stirring and dissolving, add sodium chloride 3.78g, limit is cooled to 15 DEG C with following mix and blend, preparation B liquid.
Then, limit is used silent oscillation mixer mixing A liquid and B liquid, and add in the container that water is housed of 7L on limit, reaction system is cooled to below 25 DEG C, and after stirring 5 hours, leaves standstill 30 minutes, makes solid state component sedimentation.After removing supernatant by decantation method, use filter paper to carry out suction strainer, then, use methyl alcohol and pure water to clean, filter.
After a part for the solid state component of obtained silver-colored particulate is dried to 6 hours with 40 DEG C in drying machine, pulverize, obtain the silver-colored particulate of embodiment 1-1.
The grain shape of the silver-colored particulate obtaining is granular, and carbon amount is 0.20 % by weight, average grain diameter (D
sEM) be 81.7nm, crystallite diameter D
xfor 23.8nm, polycrystallization degree (D
sEM/ D
x) be that 3.4, BET specific area value is 5.3m
2/ g, content of halogen is 690ppm, and the rate of change (150 DEG C × 30 minutes) of crystallite diameter is 138%, and the rate of change (210 DEG C × 30 minutes) of crystallite diameter is 161%.
< embodiment 2-1: the manufacture > of conductive paste
With respect to silver-colored particulate 100 weight portions of embodiment 1-1, it is 70wt% that interpolation mylar 11.0 weight portions and curing agent 1.4 weight portions, interpolation diethylene glycol monoethyl ether make the content of silver-colored particulate in conductive paste, (THINKY of Co., Ltd. produces to use rotation-revolution mixer " too youth ARE-310 of あ わ と り Practice ", registration mark) carry out premixed after, use triple-roller mill to carry out mixing, dispersion treatment equably, obtain conductive paste.
Conductive paste obtained above is coated on the polyimide film of thickness 50 μ m, heats respectively 30 minutes with 120 DEG C, 210 DEG C and 300 DEG C, obtain conductive coating.
Resistivity by obtained conductive coating when 120 DEG C of heat treated 30 minutes is 9.5 × 10
-6Ω cm, the resistivity in the time of 210 DEG C of heat treated 30 minutes is 4.1 × 10
-6Ω cm, the resistivity in the time of 300 DEG C of heat treated 30 minutes is 2.6 × 10
-6Ω cm.
Make silver-colored particulate and conductive paste according to above-described embodiment 1-1 and embodiment 2-1.Represent respectively to create conditions and the silver-colored particulate obtaining and every characteristic of conductive paste.
Embodiment 1-2～1-3 and comparative example 1-1～1-2:
By the formation condition of silver-colored particulate is carried out to various changes, obtain silver-colored particulate.
In table 1, represent creating conditions now, in table 3, represent every characteristic of the silver-colored particulate obtaining.
< embodiment 1-4: the manufacture > of silver-colored particulate
In the container that the mixed solution of first alcohol and water (methyl alcohol: water=10:1) 5.17kg is housed, add macromolecular compound " DISPERBYK-106 " (trade name, BYK Japan Co., Ltd. produces) 60g.Then, measure the concentration that contains of silver-colored particulate in the solid state component of the silver-colored particulate after cleaning, filtering of obtaining in embodiment 1-1, it is 3kg that the solid constituent of the above-mentioned silver-colored particulate of metering interpolation makes silver-colored particulate, afterwards, stir, mix 100 minutes, afterwards, distillation for removing methanol, be dried 7 hours with 30 DEG C in vacuum drier after, utilize jet pulverizer to pulverize, obtain the silver-colored particulate of embodiment 1-4.
Embodiment 1-5～1-6:
By the kind of macromolecular compound and treatment conditions are carried out to various changes, obtain silver-colored particulate.
In table 2, represent creating conditions now, in table 3, represent every characteristic of the silver-colored particulate obtaining.
[table 1]
[table 2]
[table 3]
The manufacture > of < conductive coating paint
Embodiment 2-2～2-6 and comparative example 2-1～2-2:
Except the kind of silver-colored particulate is occurred various variations, make conductive coating paint and conductive film according to the preparation method of the conductive coating paint of above-described embodiment 2-1.
In table 4, represent every characteristic of the conductive coating of creating conditions He obtaining now.
[table 4]
Utilizability in industry
The carbon content of silver-colored particulate of the present invention after due to reduction reaction is low, is suitable as the raw material that can realize conductive paste of low-firing etc.
In addition, the manufacture method of silver-colored particulate of the present invention, can reduce the carbon content of the silver-colored particulate after reduction reaction, and can obtain silver-colored particulate with high yield, therefore, is suitable as the manufacture method of the silver-colored particulate of low-temperature sintering excellence.
Claims (7)
1. a manufacture method for silver-colored particulate, is characterized in that:
The alcoholic solution (A liquid) of the amine complex of the silver nitrate that the aliphatic amine that the carbon number of preparation use silver nitrate and more than one water-soluble or water dissolvable is 2～4 makes, prepare respectively and be dissolved with ascorbic acid or arabo-ascorbic acid and the halid aqueous solution (B liquid) with described A liquid, use silent oscillation mixer that described A liquid and described B liquid are mixed, the mixture obtaining is added in the container that water is housed, stir, afterwards, obtained silver-colored particulate is cleaned, dry, wherein, in described B liquid, add 1.6 × 10 with respect to 1 equimolar silver nitrate
-3halide more than mole.
2. the silver-colored particulate being obtained by method claimed in claim 1, is characterized in that:
The carbon amount of silver particulate is below 0.25 % by weight.
3. silver-colored particulate as claimed in claim 2, is characterized in that:
By molecular weight, more than 10000 macromolecular compounds is coated the particle surface of silver particulate.
4. silver-colored particulate as claimed in claim 2 or claim 3, is characterized in that:
Average grain diameter D
sEMbelow the above 120nm of 30nm.
5. a conductive paste that contains the silver-colored particulate described in any one in claim 2～4.
6. the conductive film that right to use requires the conductive paste described in 5 to form.
7. one kind has the electronic device of conductive film claimed in claim 6.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011-289478 | 2011-12-28 | ||
| JP2011289478A JP2013139589A (en) | 2011-12-28 | 2011-12-28 | Silver fine particles, method for producing the same, and conductive paste, conductive film, and electronic device containing the silver fine particles |
| PCT/JP2012/083336 WO2013099818A1 (en) | 2011-12-28 | 2012-12-21 | Silver fine particles, production process therefor, and conductive paste, conductive membrane and electronic device, containing said silver fine particles |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104010752A true CN104010752A (en) | 2014-08-27 |
Family
ID=48697303
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201280062600.XA Pending CN104010752A (en) | 2011-12-28 | 2012-12-21 | Silver fine particles, production process therefor, conductive paste, conductive membrane and electronic device, containing said silver fine particles |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP2013139589A (en) |
| KR (1) | KR20140113910A (en) |
| CN (1) | CN104010752A (en) |
| TW (1) | TW201341087A (en) |
| WO (1) | WO2013099818A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105761778A (en) * | 2016-04-22 | 2016-07-13 | 无锡南理工科技发展有限公司 | Preparation method of low-temperature cured-type conductive silver paste |
| CN114054769A (en) * | 2021-11-17 | 2022-02-18 | 广东羚光新材料股份有限公司 | Silver micro powder and preparation method and application thereof |
| CN114054769B (en) * | 2021-11-17 | 2024-05-03 | 广东羚光新材料股份有限公司 | Silver micro powder and preparation method and application thereof |
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|---|---|---|---|---|
| JP2014098186A (en) * | 2012-11-14 | 2014-05-29 | Mitsui Mining & Smelting Co Ltd | Silver powder |
| JP6143627B2 (en) * | 2013-10-03 | 2017-06-07 | 住友金属鉱山株式会社 | Ammonia recovery method |
| CN106660129B (en) * | 2014-06-11 | 2019-08-13 | 阪东化学株式会社 | Fine silver particle dispersion, fine silver particle and its manufacturing method and bonding composition |
| TWI548472B (en) * | 2014-07-18 | 2016-09-11 | 中國鋼鐵股份有限公司 | Micro-scaled sphere silver particles and method for producing the same, conductive adhesive and electrode of solar cell |
| JP6263146B2 (en) * | 2015-04-06 | 2018-01-17 | 株式会社ノリタケカンパニーリミテド | Substrate with conductive film, method for producing the same, and conductive paste for polyimide substrate |
| WO2016166948A1 (en) * | 2015-04-17 | 2016-10-20 | バンドー化学株式会社 | Silver fine particle composition |
| JP6856350B2 (en) * | 2015-10-30 | 2021-04-07 | Ｄｏｗａエレクトロニクス株式会社 | Silver powder and its manufacturing method |
| JP7183504B2 (en) * | 2017-09-06 | 2022-12-06 | 住友金属鉱山株式会社 | Coarse particle reduction method for wet nickel powder |
| CN109465467B (en) * | 2018-12-24 | 2022-04-12 | 北京光禾生物科技有限公司 | Preparation method of liquid nano-silver |
| WO2023189993A1 (en) * | 2022-03-31 | 2023-10-05 | 日清エンジニアリング株式会社 | Silver microparticle |
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Also Published As
| Publication number | Publication date |
|---|---|
| JP2013139589A (en) | 2013-07-18 |
| WO2013099818A1 (en) | 2013-07-04 |
| KR20140113910A (en) | 2014-09-25 |
| TW201341087A (en) | 2013-10-16 |
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Application publication date: 20140827 |