WO2013018645A1 - Fines particules d'argent, pâte conductrice contenant de fines particules d'argent, film conducteur et dispositif électronique - Google Patents

Fines particules d'argent, pâte conductrice contenant de fines particules d'argent, film conducteur et dispositif électronique Download PDF

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Publication number
WO2013018645A1
WO2013018645A1 PCT/JP2012/068939 JP2012068939W WO2013018645A1 WO 2013018645 A1 WO2013018645 A1 WO 2013018645A1 JP 2012068939 W JP2012068939 W JP 2012068939W WO 2013018645 A1 WO2013018645 A1 WO 2013018645A1
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WIPO (PCT)
Prior art keywords
fine particles
silver fine
silver
crystallite diameter
less
Prior art date
Application number
PCT/JP2012/068939
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English (en)
Japanese (ja)
Inventor
山本　洋介
石谷　誠治
岩崎　敬介
峰子 大杉
森井　弘子
林　一之
康男 柿原
哲二 飯田
Original Assignee
戸田工業株式会社
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Publication date
Priority claimed from JP2011167368A external-priority patent/JP5773148B2/ja
Priority claimed from JP2011167364A external-priority patent/JP5773147B2/ja
Application filed by 戸田工業株式会社 filed Critical 戸田工業株式会社
Priority to CN201280036601.7A priority Critical patent/CN103702786B/zh
Priority to KR1020147001483A priority patent/KR20140047663A/ko
Publication of WO2013018645A1 publication Critical patent/WO2013018645A1/fr

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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
    • 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
    • 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

Definitions

  • the present invention relates to a silver fine particle having an average particle size of 100 nm or more or an average particle size of less than 100 nm, and a conductive paste, a conductive film and an electronic device containing the silver fine particle, which are suitable for use as a raw material for a conductive paste capable of low-temperature firing.
  • a silver fine particle having an average particle size of 100 nm or more or an average particle size of less than 100 nm
  • a conductive paste, a conductive film and an electronic device containing the silver fine particle which are suitable for use as a raw material for a conductive paste capable of low-temperature firing.
  • the electrodes and circuit patterns of electronic devices are formed by printing electrodes and circuit patterns on a substrate using a conductive paste containing metal particles, and then baking by heating and sintering the metal particles contained in the conductive paste. And is classified into a firing paste and a polymer paste according to the heating and firing temperature. In recent years, the heating and firing temperature tends to be lowered.
  • the fired paste is generally used for ceramic substrates, and is mainly composed of metal particles, glass frit, a solvent and the like, and the heating and firing temperature thereof is about 500 ° C. or higher.
  • polymer type paste is used for membrane wiring boards, conductive adhesives, etc., and consists of a paste in which metal particles are dispersed in a resin, a curing agent, an organic solvent, a dispersing agent, etc.
  • a predetermined conductor pattern is formed on a substrate by printing or the like, and is heated and fired at a temperature up to about 250 ° C. for use.
  • silver is used as the conductive particles in the conductive paste for screen printing used for forming the circuit of the membrane wiring board.
  • Silver has a drawback that it tends to cause migration, but it is difficult to oxidize compared to copper having the same specific resistance, so it is easy to handle and is widely used.
  • a polyimide flexible substrate is generally used because it can be heated up to about 300 ° C. and has excellent heat resistance.
  • Inexpensive PET (polyethylene terephthalate) substrates and PEN (polyethylene naphthalate) substrates are being investigated as alternative materials.
  • PET substrates and PEN substrates have lower heat resistance than polyimide flexible substrates, and in particular, PET film substrates used for membrane wiring boards need to be heated and fired at 150 ° C. or lower.
  • heating and firing can be performed at a temperature lower than 200 ° C., it becomes possible to form electrodes and circuit patterns on a substrate such as polycarbonate and paper, and it is expected that the use of various electrode materials will be expanded.
  • metal particle that is a raw material for such a conductive paste that can be fired at a low temperature silver fine particles of nanometer order are expected.
  • the reason for this is that when the size of the metal particles is on the order of nanometers, the surface activity becomes high and the melting point is much lower than that of the bulk metal, so that it can be sintered at a low temperature. .
  • nanometer-order silver fine particles can be sintered at low temperatures, and heat resistance is maintained once sintered, which is also expected as a lead-free solder replacement material using a property not found in conventional solder. Has been.
  • silver fine particles of submicron to micron size have been proposed as silver fine particles that can be used for wiring materials and electrode materials of electronic devices, and silver fine particles that can be fired at low temperature.
  • Spherical silver powder with limited ratio Patent Document 1
  • average particle diameter, crystallite diameter and silver fine particles with limited ratio of average particle diameter to crystallite diameter Patent Document 2
  • tap density laser diffraction method average particle diameter
  • silver powder with a specific surface area limited Patent Document 3
  • a method for producing silver fine particles having an average primary particle diameter of 0.05 to 1.0 ⁇ m and a crystallite diameter of 20 to 150 nm Patent Document 4
  • spherical silver powder having a sharp particle size distribution and high dispersibility Patent Document 5
  • primary particle size 0.07 to 4.5 ⁇ m
  • crystallite size of 20 nm or more Crystal silver powder Patent Document 6
  • the silver fine particles disclosed in Patent Document 1 to Patent Document 6 are all limited in average particle diameter, crystallite diameter, BET specific surface area value, etc., but the Miller index (111) by X-ray diffraction is limited. And the ratio of the crystallite diameter in (200) [crystallite diameter D X (111) / crystallite diameter D X (200)] is not taken into consideration.
  • X (111) / crystallite diameter D X (200)] is less than 1.40, it is difficult to obtain silver fine particles having good low-temperature sinterability.
  • the crystallite diameter D X (111) exceeds 20 nm, the crystallite diameter of the silver fine particles is large, so that the reactivity inside the silver fine particles is low, which is disadvantageous for low-temperature sintering.
  • a technical problem of the present invention is to provide silver fine particles suitable as a raw material for conductive paste that can be fired at a low temperature. Further, the average particle diameter of the obtained silver fine particles is in a wide range, and it is particularly desirable to obtain silver fine particles of 30 nm or more and less than 100 nm and 100 nm or more and less than 1 ⁇ m.
  • the ratio of the crystallite diameter in the Miller indices (111) and (200) by X-ray diffraction is 1.40 or more.
  • Silver fine particles characterized by the present invention (Invention 1).
  • this invention is a silver fine particle of this invention 1 whose average particle diameter (DSEM ) is 100 nm or more and less than 1 micrometer (invention 2).
  • the present invention is the silver fine particle according to the first or second aspect of the present invention, wherein the crystallite diameter D X (111) at the Miller index (111) is 20 nm or less (Invention 3).
  • the present invention is the silver fine particles according to any one of the present inventions 1 to 3, wherein the crystallite diameter D X (200) at the Miller index (200) is 14 nm or less (Invention 4).
  • the present invention is the invention according to any one of the present inventions 1 to 4, wherein the particle surface of the silver fine particles is coated with one or more kinds selected from polymer dispersants having a number average molecular weight of 1,000 or more. Silver fine particles (Invention 5).
  • this invention is a silver fine particle of this invention 1 whose average particle diameter (D SEM ) is 30 nm or more and less than 100 nm (this invention 6).
  • the present invention is the silver fine particles according to the first or sixth aspect of the present invention, wherein the crystallite diameter D X (111) at the Miller index (111) is 25 nm or less (Invention 7).
  • the present invention is the silver fine particles according to any one of the present inventions 1, 6, and 7 having a crystallite diameter D X (200) of Miller index (200) of 15 nm or less (Invention 8).
  • the present invention is the silver fine particles according to any one of claims 1 and 6 to 8, wherein the surface of the silver fine particles is coated with a polymer compound having a molecular weight of 10,000 or more (Invention 9).
  • present invention is a conductive paste containing the silver fine particles according to any one of claims 1 to 9 (present invention 10).
  • the present invention is a conductive film formed using the conductive paste according to claim 10 (Invention 11).
  • the present invention also provides an electronic device having the conductive film according to claim 11 (present invention 11).
  • the silver fine particles according to the present invention have a crystallite diameter ratio [crystallite diameter D X (111) / crystallite diameter D X (200)] of 1.40 and Miller index (111) by X-ray diffraction of 1.40. Because of the above, it is suitable as a raw material for conductive paste and the like that can be fired at a low temperature.
  • the silver fine particles according to the present invention have a crystallite diameter ratio [crystallite diameter D X (111) / crystallite diameter D X (200)] of 1.40 and Miller index (111) by X-ray diffraction of 1.40. Silver fine particles characterized by the above.
  • the average particle size of the silver fine particles of the present invention can be determined over a wide range depending on the conditions required for the application. From the viewpoint of the production method, the average particle size (D SEM ) is 100 nm or more (first embodiment). And an average particle diameter (D SEM ) of less than 100 nm (second embodiment).
  • the average particle size (D SEM ) of the silver fine particles according to the present invention is 100 nm or more, preferably 100 nm or more and less than 1 ⁇ m, more preferably 100 to 500 nm.
  • the average particle diameter (D SEM ) is in the above range, it is easy to cope with finer wiring and electrodes.
  • the average particle size (D SEM ) is less than 100 nm, sintering is likely to occur even at room temperature, and the dispersibility and dispersion stability in the conductive paste tend to be reduced. Prescribing may be required.
  • the average particle diameter (D SEM ) exceeds 1 ⁇ m, the sinterability at low temperatures is lowered, which is not preferable.
  • the particle size is too large, it is difficult to refine an electronic device obtained using the particle size.
  • Ratio of crystallite diameter in Miller index (111) and (200) by X-ray diffraction of silver fine particles according to the first aspect of the present invention [crystallite diameter D X (111) / crystallite diameter D X (200)] Is 1.40 or more, preferably 1.44 or more, more preferably 1.48 or more.
  • the ratio of the crystallite diameter D X (111) to the crystallite diameter D X (200) is 1.40 or more, silver fine particles having excellent low-temperature sinterability can be obtained.
  • the crystallite diameter D X (111) in the Miller index (111) by X-ray diffraction of the silver fine particles according to the first aspect of the present invention is preferably 20 nm or less, more preferably 10 to 19 nm, still more preferably. 10 to 18 nm.
  • the crystallite diameter D X (111) exceeds 20 nm, the reactivity in the silver fine particles is lowered, and the low-temperature sinterability is impaired.
  • the crystallite diameter D X (111) is less than 10 nm, the silver fine particles become unstable and partial sintering and fusion start even at room temperature, which is not preferable.
  • the crystallite diameter D X (200) in the Miller index (200) by X-ray diffraction of the silver fine particles according to the first aspect of the present invention is preferably 14 nm or less, more preferably 13 nm or less, still more preferably 12 nm. It is as follows.
  • the crystallite diameter D X (200) is preferably smaller so that [crystallite diameter D X (111) / crystallite diameter D X (200)] is 1.40 or more.
  • the low-temperature sinterability of the silver fine particles according to the first aspect of the present invention is the change rate of the crystallite diameter by heating described later [(crystallite diameter of silver fine particles after heating at 150 ° C. for 30 minutes / silver fine particles before heating Crystallite diameter) ⁇ 100], and the change rate of the crystallite diameter by heating at 150 ° C. is preferably 120% or more, more preferably 125% or more. When the change rate of the crystallite diameter is less than 120%, it cannot be said that the low-temperature sinterability is excellent. In the present invention, when heated at 210 ° C. for 30 minutes, the change rate of the crystallite diameter is preferably 150% or more, and more preferably 170% or more.
  • the BET specific surface area value of the silver fine particles according to the first aspect of the present invention is preferably 5 m 2 / g or less. When the BET specific surface area value exceeds 5 m 2 / g, the viscosity of the conductive paste obtained by using this is not preferable.
  • the average particle diameter (D SEM ) of the silver fine particles according to the second aspect of the present invention is less than 100 nm, preferably 30 nm or more and less than 100 nm, more preferably 35 nm or more and less than 100 nm.
  • D SEM average particle diameter
  • the average particle diameter (D SEM ) is in the above range, it is easy to refine an electronic device obtained using the average particle diameter (D SEM ).
  • the average particle size (D SEM ) is less than 30 nm, the surface activity of the silver fine particles increases, and it is not preferable because a large amount of organic matter or the like needs to be adhered in order to stably maintain the fine particle size. .
  • Ratio of crystallite diameter in Miller index (111) and (200) by X-ray diffraction of silver fine particles according to the second aspect of the present invention [crystallite diameter D X (111) / crystallite diameter D X (200)] Is 1.40 or more, preferably 1.44 or more, more preferably 1.48 or more.
  • the ratio of the crystallite diameter D X (111) to the crystallite diameter D X (200) is 1.40 or more, silver fine particles having excellent low-temperature sinterability can be obtained.
  • the crystallite diameter D X (111) in the Miller index (111) by X-ray diffraction of the silver fine particles according to the second aspect of the present invention is preferably 25 nm or less, more preferably 23 to 10 nm, still more preferably 20 to 10 nm.
  • the crystallite diameter D X (111) exceeds 25 nm, the reactivity in the silver fine particles is lowered, and the low-temperature sinterability is impaired.
  • the crystallite diameter D X (111) is less than 10 nm, the silver fine particles become unstable and partial sintering and fusion start even at room temperature, which is not preferable.
  • the crystallite diameter D X (200) in the Miller index (200) by X-ray diffraction of the silver fine particles according to the second aspect of the present invention is preferably 15 nm or less, more preferably 14 nm or less, still more preferably 13 nm. It is as follows.
  • the crystallite diameter D X (200) is preferably smaller so that [crystallite diameter D X (111) / crystallite diameter D X (200)] is 1.40 or more.
  • the low-temperature sinterability of the silver fine particles according to the second aspect of the present invention is the change rate of crystallite diameter by heating described later [(crystallite diameter of silver fine particles after heating at 150 ° C. for 30 minutes / silver fine particles before heating (Crystallite diameter) ⁇ 100], and the change rate of the crystallite diameter by heating at 150 ° C. is preferably 150% or more, more preferably 160% or more. When the change rate of the crystallite diameter is less than 150%, it cannot be said that the low-temperature sinterability is excellent. In the present invention, when heated at 210 ° C. for 30 minutes, the change rate of the crystallite diameter is preferably 180% or more, and more preferably 200% or more.
  • the BET specific surface area value of the silver fine particles according to the second aspect of the present invention is preferably 10 m 2 / g or less, more preferably 8 m 2 / g or less.
  • the BET specific surface area value exceeds 10 m 2 / g, the viscosity of the conductive paste obtained by using this is not preferable.
  • the particle shape of the silver fine particles according to the first and second aspects of the present invention is preferably spherical or granular.
  • the silver fine particles of the present invention are preferably coated with one or more selected from polymer dispersants.
  • the polymer dispersant is properly used depending on the number average molecular weight.
  • the particle surface of the silver fine particles is preferably coated with one or more selected from polymer dispersing agents having a number average molecular weight of 1,000 or more.
  • the number average molecular weight of the dispersant is preferably 1,000 or more, more preferably 1,000 to 150,000, and still more preferably 5,000 to 100,000.
  • the silver fine particle powder obtained by surface-treating a dispersant having a number average molecular weight of less than 1,000 has an insufficient effect of treating the dispersant, and silver fine particles tend to aggregate in the subsequent pulverization treatment.
  • the number average molecular weight exceeds 150,000, the viscosity of the dispersant becomes high, and it becomes difficult to uniformly treat the surface of the silver fine particles.
  • the surface of the silver fine particles is preferably coated with a polymer compound (polymer dispersing agent) having a molecular weight of 10,000 or more.
  • a polymer compound polymer dispersing agent
  • the molecular weight is less than 10,000, agglomerates are produced in the subsequent pulverization treatment, and the resulting silver fine particles are not preferable because dispersibility in the conductive paste becomes difficult.
  • the upper limit of the molecular weight of the polymeric dispersant is about 100,000. If the molecular weight is higher than this, the viscosity increases, and uniform processing on the surface of the silver fine particles becomes difficult.
  • the dispersant has both an acid value and an amine value. It is preferable to use a dispersant (having both an acidic functional group and a basic functional group) or a dispersant having an acid value and a dispersant having an amine value in combination.
  • the coating amount of the dispersant is preferably 0.1 to 3.0% by weight, more preferably 0.2 to 2.5% by weight based on the silver fine particle powder, although it depends on the BET surface area value of the silver fine particles. .
  • the amount is less than 0.1% by weight, the amount of the dispersant is insufficient, and the silver fine particle powder tends to aggregate in the subsequent pulverization treatment.
  • the amount exceeds 3.0% by weight, aggregation of the silver fine particle powder can be suppressed, but an organic component not involved in conductivity increases, which is not preferable.
  • polymer dispersant those commercially available as pigment dispersants can be used, and specifically, 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-142, DISPERBYK-142, DISPERBYK-142, DISPERBYK-142 -162, DISPERBYK-163, DISPERBYK-164, DISPERBYK-166, D SPERBYK-167, DISPERBYK-168, DISPERBYK-170, DISPERBYK-171, DISPERBYK-
  • the silver fine particles according to the present invention are prepared by adding a reducing agent-containing aqueous solution to a silver salt complex-containing aqueous solution to reduce and precipitate silver fine particles, or by adding a silver nitrate aqueous solution to a reducing solution and reducing and precipitating silver fine particles. It can be obtained by any method for producing silver fine particles.
  • a method for producing silver fine particles having an average particle diameter (D SEM ) of less than 100 nm according to the second aspect of the present invention a solvent reaction in which an alcohol solution of a silver salt complex is added to a reducing agent solution to reduce and precipitate silver fine particles.
  • a method for producing silver fine particles in the system can also be adopted. In any case, it is important to perform all steps from reaction to drying in a temperature range of 30 ° C. or lower.
  • the silver salt complex-containing aqueous solution and the reducing agent-containing aqueous solution are respectively prepared in advance.
  • the silver salt complex in the present invention can be obtained by mixing silver nitrate or silver acetate as a silver raw material with aqueous ammonia, ammonium salt or chelate compound.
  • aqueous ammonia, ammonium salt or chelate compound As the addition amount of ammonia, since the coordination number of ammonia in the ammine complex is 2, it is preferable to add 2 mol or more of ammonia to 1 mol of silver.
  • the amount of ammonia added is more preferably at least 4 mol, and even more preferably at least 10 mol per mol of silver.
  • erythorbic acid ascorbic acid, alkanolamine, hydroquinone, glucose, pyrogallol, hydrazine, hydrogen peroxide and formaldehyde
  • an organic reducing agent is preferably used, and more preferably erythorbic acid or ascorbic acid.
  • the amount of reducing agent added is preferably 1.0 mol or more, and more preferably 1.0 to 2.0 mol, per 1 mol of silver.
  • the amount exceeding 2.0 moles relative to 1 mole of silver is not preferable because the generated silver fine particles tend to aggregate.
  • the reducing solution and the silver nitrate aqueous solution are prepared in advance.
  • the aqueous silver nitrate solution in the present invention can be obtained by mixing silver nitrate with ion-exchanged water or pure water.
  • the concentration of silver nitrate in the aqueous solution is preferably in the range of 0.08 to 2.0 mol / l, more preferably 0.1 to 1.8 mol / l.
  • the reducing solution can be obtained by mixing and stirring ammonia water and ion exchange water or pure water and a reducing agent.
  • a reducing agent used for a reducing liquid the above-mentioned reducing agent can be used.
  • the amount of reducing agent added is preferably 1.0 mol or more, and more preferably 1.0 to 2.0 mol, per 1 mol of silver.
  • the amount exceeding 2.0 moles relative to 1 mole of silver is not preferable because the generated silver fine particles tend to aggregate.
  • the liquid temperature is kept at 18 ° C. or lower, and a silver salt complex-containing aqueous solution and a reducing agent-containing aqueous solution or a reducing solution and a silver nitrate aqueous solution are used. It is preferable to adjust so that the liquid temperature does not exceed 20 ° C. when mixing and stirring.
  • the reaction temperature exceeds 20 ° C., the crystallite diameter D X (111) of the silver fine particles increases, and the ratio of crystallite diameter D X (111) / crystallite diameter D X (200) is 1.40. This is not preferable because the low temperature sinterability is impaired.
  • the addition of the reducing agent-containing aqueous solution to the silver salt complex-containing aqueous solution or the addition of the silver nitrate aqueous solution to the reducing solution is preferably performed in as short a time as possible, more preferably within 20 seconds, and even more preferably within 15 seconds. is there.
  • the addition time of the reducing agent-containing aqueous solution to the silver salt complex-containing aqueous solution or the addition time of the silver nitrate aqueous solution to the reducing solution is prolonged, the generated silver fine particles are aggregated to increase the particle size and the particle size distribution. There is a tendency.
  • the silver fine particle cake obtained was redispersed in a hydrophilic organic solvent, and the water on the surface of the silver fine particles was replaced with a hydrophilic organic solvent. Dry using vacuum drying. When the drying temperature exceeds 30 ° C., the crystallite diameter D X (111) of the silver fine particles increases, and the ratio of crystallite diameter D X (111) / crystallite diameter D X (200) is 1.40. This is not preferable because the low temperature sinterability is impaired. By replacing the water on the surface of the silver fine particles with a hydrophilic organic solvent, it is possible to prevent the silver fine particles after drying from being firmly agglomerated with each other, and subsequent grinding treatment or surface treatment / grinding treatment, etc. It becomes easy.
  • hydrophilic organic solvent examples include methanol, ethanol and propanol, acetone and the like. Considering removal of the solvent by drying, methanol and ethanol are preferred.
  • silver fine particles having any of the average particle diameters of the first and second embodiments can be produced.
  • a method for controlling the particle diameter adjustment of the concentration of silver nitrate in the aqueous silver nitrate solution or Adjustment of the ammonia water concentration in the reducing solution can be mentioned.
  • the silver fine particles having the average particle diameter of the first aspect can be produced mainly.
  • the silver nitrate in the aqueous silver nitrate solution can be mainly produced by lowering the concentration of the aqueous solution and increasing the concentration of the ammonia water in the reducing solution.
  • the alcohol solution of a silver salt complex in a solvent reaction system in which an alcohol solution of a silver salt complex is added to a reducing agent solution to reduce and precipitate silver fine particles is water-soluble or water-soluble with silver nitrate in the alcohol solution and has 2 to 2 carbon atoms. It can be obtained by mixing one or more of the four aliphatic amines.
  • the aliphatic amine is preferably 2.0 to 2.5 moles, more preferably 2.0 to 2.3 moles per mole of silver nitrate. When the amount of the aliphatic amine is less than 2.0 mol with respect to 1 mol of silver nitrate, large grains tend to be generated.
  • aliphatic amine having 2 to 4 carbon atoms it is important to use a water-soluble or water-soluble aliphatic amine, specifically, ethylamine, n-propylamine, iso-propylamine, n-butylamine, iso- Butylamine and the like can be used, but n-propylamine and n-butylamine are preferable in view of the low-temperature sintering property and handling property of the silver fine particles.
  • alcohols in the solvent reaction system those having compatibility with water can be used. Specifically, methanol, ethanol, propanol, isopropanol, and the like can be used, and methanol and ethanol are preferable. These alcohols may be used alone or in combination.
  • the reducing agent solution in the solvent reaction system can be obtained by dissolving ascorbic acid or erythorbic acid in water, or dissolving ascorbic acid or erythorbic acid in water and then adding alcohol and mixing.
  • Ascorbic acid or erythorbic acid is preferably 1.0 to 2.0 moles, more preferably 1.0 to 1.8 moles per mole of silver nitrate.
  • ascorbic acid or erythorbic acid exceeds 2.0 mol with respect to 1 mol of silver nitrate, the generated silver fine particles tend to aggregate, which is not preferable.
  • the addition of the alcohol solution of the silver salt complex to the reducing agent solution in the solvent reaction system is performed by dropping the alcohol solution of the silver salt complex into the reducing solution.
  • the reaction temperature in the reduction reaction is in the range of 15 to 30 ° C., more preferably 18 to 30 ° C. When the reaction temperature exceeds 30 ° C., the crystallite size increases, which is not preferable.
  • the dropping rate is preferably 3 ml / min or less. When the dropping time is short, the particle size and the crystallite size tend to increase, which is not preferable.
  • the silver fine particles of the present invention can be obtained by drying the washed silver fine particles at a temperature of 30 ° C. or lower or by vacuum drying and then pulverizing them by a conventional method.
  • the drying temperature exceeds 30 ° C.
  • the crystallite diameter D X (111) of the silver fine particles increases, and the ratio of crystallite diameter D X (111) / crystallite diameter D X (200) is 1.40. This is not preferable because the low temperature sinterability is impaired.
  • the silver fine particles of the present invention can be obtained by pulverizing the silver fine particles after drying by a conventional method.
  • the silver fine particles according to the present invention are preferably subjected to a surface treatment with a polymer dispersant before the pulverization treatment.
  • a surface treatment with a polymer dispersant before the pulverization treatment.
  • the coating amount with a polymer compound having a molecular weight of 1,000 or more is preferably 0.1 to 3.0% by weight, more preferably 0.2 to 2.5% by weight, based on the silver fine particles.
  • the coating amount with a polymer compound having a molecular weight of 10,000 or more is preferably 0.2 to 4% by weight, more preferably 0.3 to 3% by weight, based on the silver fine particles.
  • the treatment amount with the polymer compound is within the above range, a sufficient treatment effect by the pulverization treatment can be obtained.
  • the surface treatment of the silver fine particles with the polymer compound is carried out by redispersing the silver fine particles after substitution and drying with a hydrophilic organic solvent in a polymer compound solution obtained by dissolving the polymer compound in the organic solvent, for 30 to 300 minutes. After gently stirring, the organic solvent is removed, and drying is performed at 30 ° C. or lower using a dryer or vacuum drying.
  • the conductive paste according to the present invention may be in any form of a fired paste and a polymer paste.
  • the conductive paste is composed of the silver fine particles and the glass frit according to the present invention.
  • Other components may be blended.
  • a polymer type paste it consists of silver fine particles and a solvent according to the present invention, and if necessary, other components such as a binder resin, a curing agent, a dispersant, and a rheology modifier may be blended.
  • binder resin those known in the art can be used.
  • cellulose resins such as ethyl cellulose and nitrocellulose
  • various modified materials such as polyester resins, urethane modified polyester resins, epoxy modified polyester resins, and acrylic modified polyesters.
  • These binder resins can be used alone or in combination of two or more.
  • solvent those known in the art can be used, and examples thereof include tetradecane, toluene, xylene, ethylbenzene, diethylbenzene, isopropylbenzene, amylbenzene, p-cymene, tetralin, and petroleum aromatic hydrocarbon mixtures.
  • Hydrocarbon solvents ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-butyl ether, propylene glycol mono-t-butyl ether, diethylene glycol monoethyl ether, diethylene glycol Monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monobutyl ether, tri Ether or glycol ether solvents such as propylene glycol monomethyl ether; glycol ester solvents such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate Ketone solvents such as methyl isobutyl ketone and cyclohexanone; terpen
  • the content of silver fine particles in the conductive paste varies depending on the application, but it is preferably as close to 100% by weight as possible, for example, in the case of wiring formation.
  • the conductive paste according to the present invention is obtained by mixing and dispersing each component using various kneaders and dispersers such as a laika machine, a pot mill, a three roll mill, a rotary mixer, a twin screw mixer, and the like. Can do.
  • the conductive paste according to the present invention can be applied to various coating methods such as screen printing, ink jet method, gravure printing, transfer printing, roll coating, flow coating, spray coating, spin coating, dipping, blade coating, and plating.
  • the conductive paste according to the present invention is used for forming electrodes such as FPD (flat panel display), solar cell, organic EL, wiring for LSI substrates, and wiring for filling fine trenches, via holes, contact holes, etc. It can be used as a material.
  • FPD flat panel display
  • organic EL organic EL
  • wiring for LSI substrates and wiring for filling fine trenches, via holes, contact holes, etc.
  • It can be used as a material.
  • FPD flat panel display
  • organic EL organic EL
  • the important point in the present invention is that the ratio of the crystallite diameter in the Miller indices (111) and (200) by X-ray diffraction [crystallite diameter D X (111) / crystallite diameter D X (200)] is 1.40. This is the fact that the silver fine particles described above can be fired at a low temperature.
  • the average particle diameter of the silver fine particles is (D SEM ), preferably 30 nm or more and less than 1 ⁇ m, and a very wide range of average particle diameters can be selected.
  • the silver fine particles according to the present invention are excellent in low-temperature sinterability is unclear, but as a result of many experiments conducted by the present inventors, the silver fine particles excellent in low-temperature sinterability are all crystalline. It has been found that the ratio of crystal diameters [crystallite diameter D X (111) / crystallite diameter D X (200)] has a value of 1.40 or more. This is considered to indicate that the larger the ratio of the crystallite diameter D X (111) and the crystallite diameter D X (200), the more unstable the crystal lattice is, and the more unstable the silver fine particles are. It is done.
  • Examples 1-1 to 1-9, Comparative Examples 1-1 to 1-5, Examples 2-1 to 2-9, Comparative Examples 2-1 to 2-5, and Examples Examples 3-1 to 3-9 and comparative examples 3-1 to 3-5 are examples in the first aspect of the present invention.
  • Examples 5-1 to 5-13 and Comparative examples 5-1 to 5-7 are examples in the first aspect of the present invention.
  • the average particle diameter of the silver fine particles was obtained by taking a photograph of the particles using a scanning electron micrograph “S-4800” (manufactured by HITACHI), measuring the particle diameter of 100 or more particles using the photograph, The value was calculated and taken as the average particle size (D SEM ).
  • the specific surface area of the silver fine particles was represented by a value measured by BET method using “Monosorb MS-11” (manufactured by Kantachrome Co., Ltd.).
  • the crystallite diameter D X (111) and the crystallite diameter D X (200) of the silver fine particles are obtained by using an X-ray diffractometer “RINT2500” (manufactured by Rigaku Corporation) and a plane index using Cu K ⁇ rays as a radiation source.
  • the half widths of the peaks on the (1, 1, 1) plane and the (2, 0, 0) plane were obtained, and the crystallite diameter was calculated from the Scherrer equation.
  • the ratio of the crystallite diameter in the Miller index (111) and (200) by X-ray diffraction of the silver fine particles is the above-mentioned crystallite diameter D X (111) and crystallite diameter D X (200). D X (111) / crystallite diameter D X (200)].
  • Rate of change of the crystallite diameter by heating the silver particles is the crystallite size after the fine silver particles were heated at 0.99 ° C. 30 min D X of silver particles before heating (111) crystallite diameter D X (111 ) And calculated according to the following formula 1. Note that the rate of change in crystallite diameter was determined in the same manner when the heating condition was changed to 210 ° C. for 30 minutes.
  • the characteristics of the conductive coating film using the firing paste in the example of the first aspect of the present invention were determined by the following method. That is, a baking type conductive paste described later is applied on an alumina substrate, pre-dried at 120 ° C. for 30 minutes, and then heated at 200 ° C., 300 ° C., 400 ° C., 500 ° C., and 600 ° C. for 30 minutes.
  • the measured conductive film was measured using a four-terminal electrical resistance measuring device “Loresta GP / MCP-T600” (manufactured by Mitsubishi Chemical Analytech Co., Ltd.), and the specific resistance was calculated from the sheet resistance and film thickness.
  • the specific resistance of the conductive coating film in the example of the first aspect of the present invention is such that the conductive paste described later is applied on a polyimide film, preliminarily dried at 120 ° C., and then 150 ° C., 210 ° C. and 300 ° C.
  • Each conductive film obtained by heating and curing at each temperature for 30 minutes was measured using a four-terminal electrical resistance measuring device “Loresta GP / MCP-T600” (manufactured by Mitsubishi Chemical Analytech Co., Ltd.), and sheet resistance The specific resistance was calculated from the film thickness.
  • Example 1-1 Production of silver fine particles> After adding 739 g of erythorbic acid (1.5 mol with respect to 1 mol of silver), 32.3 L of pure water and 780 g of ammonia water (25%) (4.1 mol with respect to 1 mol of silver) as a reducing agent to a 50 L reaction tower, While reducing to 18 ° C. or lower, mixing and stirring were performed to prepare a reducing solution. Separately, 475 g of silver nitrate and 6,300 g of pure water were added to a 20 mL plastic container, and then mixed and stirred while cooling to 18 ° C. or lower to prepare a silver nitrate aqueous solution.
  • an aqueous silver nitrate solution was added to the reducing solution while stirring (addition time was 10 seconds or less). After completion of the addition, the mixture was stirred for 30 minutes and then allowed to stand for 30 minutes to precipitate the solid matter. After removing the supernatant by decantation, the filtrate was suction filtered using a filter paper, and then washed and filtered using pure water until the conductivity of the filtrate reached 7 ⁇ S / cm.
  • the obtained silver fine particle cake was redispersed in a methanol solution, the water on the surface of the silver fine particles was replaced with methanol, filtered, and dried in a vacuum dryer at 25 ° C. for 6 hours.
  • a polymer compound “DISPERBYK-106” (trade name: manufactured by Big Chemie Japan Co., Ltd.) was dispersed in a liquid for mixing pure water and methanol (water: methanol ratio 1:10).
  • 300 g of the obtained silver fine particles were added (0.8 wt% with respect to the silver fine particles), dried in a vacuum dryer at 25 ° C. for 12 hours, and then pulverized by a jet type pulverizer. Silver fine particles were obtained.
  • the obtained silver fine particles have a granular shape, an average particle diameter (D SEM ) of 268 nm, a crystallite diameter D X (111) of 14.2 nm, a crystallite diameter D X (200) of 9.0 nm, D X ( 111) / D X (200) is 1.58, BET specific surface area value is 1.5 m 2 / g, change rate of crystallite diameter (150 ° C. ⁇ 30 minutes) is 128%, change rate of crystallite diameter (210 ° C. ⁇ 30 minutes) was 179%.
  • Example 2-1 Production of conductive paste (fired paste)> Silver fine particles of Example 1-1 2.5 parts by weight of ethyl cellulose resin, 2.5 parts by weight of lead-free glass frit, 3.0 parts by weight of dinormal butyl phthalate and texanol / 1-phenoxy-2- After adding 15.4 parts by weight of propanol (1: 1) and performing premixing using a rotating / revolving mixer “Awatori Nertaro ARE-310” (registered trademark, manufactured by Sinky Corporation), three rolls The mixture was uniformly kneaded and dispersed to obtain a conductive paste (fired paste) of Example 2-1.
  • the conductive paste (baked paste) obtained above is applied onto an alumina substrate, pre-dried at 120 ° C. for 30 minutes, and then heated at 200 ° C., 300 ° C., 400 ° C., 500 ° C., and 600 ° C. for 30 minutes. As a result, a conductive coating film was obtained.
  • the temperature at which the sheet specific resistance of the obtained conductive coating film was 1.0 ⁇ 10 ⁇ 5 ⁇ ⁇ cm or less was 195 ° C.
  • the specific resistance when heat-treated at 120 ° C. for 30 minutes is 7.7 ⁇ 10 ⁇ 5 ⁇ ⁇ cm, and the specific resistance when heat-treated at 200 ° C. for 30 minutes is 9.1 ⁇ 10 ⁇ 6 ⁇ ⁇ cm.
  • the specific resistance was 4.7 ⁇ 10 ⁇ 6 ⁇ ⁇ cm when heat-treated at 400 ° C. for 30 minutes.
  • Example 3-1 Production of conductive paste (polymer type paste)> 11.0 parts by weight of polyester resin and 1.4 parts by weight of curing agent with respect to 100 parts by weight of silver fine particles of Example 1-1, and diethylene glycol monoethyl so that the content of silver fine particles in the conductive paste is 70 wt%. After adding ether and premixing, the mixture was uniformly kneaded and dispersed using three rolls to obtain the conductive paste of Example 3-1.
  • the conductive paste (polymer type paste) obtained above was applied onto a polyimide film having a thickness of 50 ⁇ m and heated at 120 ° C., 210 ° C. and 300 ° C. for 30 minutes, respectively, to obtain a conductive coating film.
  • the specific resistance when the obtained conductive film is heat-treated at 120 ° C. for 30 minutes is 3.7 ⁇ 10 ⁇ 4 ⁇ ⁇ cm, and the specific resistance when heat-treated at 210 ° C. for 30 minutes is 2.8. ⁇ a 10 -6 ⁇ ⁇ cm, the specific resistance in the case of heat treatment at 300 ° C. 30 minutes was 9.8 ⁇ 10 -6 ⁇ ⁇ cm.
  • Silver fine particles and a conductive paste were prepared according to Example 1-1, Example 2-1, and Example 3-1. Various characteristics of each production condition and the obtained silver fine particle powder and electric paste are shown.
  • the particles of Comparative Example 1-5 are commercially available micron-sized silver particle powders.
  • Example 1-6 Production of silver fine particles> After adding 595 g of silver nitrate, 38 L of pure water and 2,381 g of ammonia water (25%) (10.0 mol to 1 mol of silver) as a silver raw material to a 50 L reaction tower, the mixture was mixed while cooling to 10 ° C. or less. Stirring was performed to prepare a silver salt complex aqueous solution. Separately, after adding 925 g of erythorbic acid (1.5 mol with respect to 1 mol of silver) and 8,333 g of pure water as a reducing agent to a 20 L plastic container, mixing and stirring are performed while cooling to 10 ° C. or less. A reducing agent-containing aqueous solution was prepared.
  • the reducing agent-containing aqueous solution was added to the silver salt complex aqueous solution with stirring while cooling the reaction system to 10 ° C. or less (addition time was 10 seconds or less). After completion of the addition, the mixture was stirred for 30 minutes and then allowed to stand for 30 minutes to precipitate the solid matter. After removing the supernatant by decantation, the filtrate was suction filtered using a filter paper, and then washed and filtered using pure water until the electric conductivity of the filtrate reached 20 ⁇ S / cm.
  • the obtained silver fine particle cake was redispersed in a methanol solution, the water on the surface of the silver fine particles was replaced with methanol, filtered, and dried in a vacuum dryer at 25 ° C. for 6 hours.
  • 3.6 g of a polymer compound “DISPERBYK-106” (trade name: manufactured by Big Chemie Japan Co., Ltd.) was dispersed in a pure water / methanol mixture (water: methanol ratio 1:10).
  • 300 g of the obtained silver fine particles were added (1.2% by weight based on the silver fine particles), dried in a vacuum dryer at 25 ° C. for 12 hours, and then pulverized by a jet type pulverizer.
  • Silver fine particles were obtained.
  • Table 4 shows the manufacturing conditions and various characteristics of the obtained conductive coating film.
  • Table 5 shows the manufacturing conditions and various characteristics of the obtained conductive coating film.
  • Example 4-1 Production of silver fine particles> After adding 739 g of erythorbic acid (1.5 mol with respect to 1 mol of silver), 33.4 L of pure water and 3,808 g of ammonia water (25%) (20 mol with respect to 1 mol of silver) as a reducing agent to a 50 L reaction tower, While reducing to 18 ° C. or lower, mixing and stirring were performed to prepare a reducing solution. Separately, 475 g of silver nitrate and 1,900 g of pure water were added to a 20 L plastic container, and then mixed and stirred while cooling to 18 ° C. or lower to prepare a silver nitrate aqueous solution.
  • an aqueous silver nitrate solution was added to the reducing solution while stirring (addition time was 10 seconds or less). After completion of the addition, the mixture was stirred for 30 minutes and then allowed to stand for 30 minutes to precipitate the solid matter. After removing the supernatant by decantation, the filtrate was suction filtered using filter paper, and then washed and filtered using pure water until the conductivity of the filtrate reached 38 ⁇ S / cm.
  • the obtained silver fine particle cake was redispersed in a methanol solution, the water on the surface of the silver fine particles was replaced with methanol, filtered, and dried in a vacuum dryer at 25 ° C. for 6 hours.
  • 4.2 g of a polymer compound “DISPERBYK-106” (trade name: manufactured by Big Chemie Japan Co., Ltd.) dispersed in a methanol solution was added to 300 g of the obtained silver fine particles (1 per silver fine particle). 4% by weight) and after stirring and mixing for 90 minutes, the methanol was distilled off.
  • the fine particles of Example 4-1 were obtained by pulverization with a jet pulverizer.
  • the obtained silver fine particles have a granular shape, the average particle diameter (D SEM ) is 86.0 nm, the crystallite diameter D X (111) is 15.4 nm, the crystallite diameter D X (200) is 9.5 nm, D X (111) / D X (200) is 1.62, BET specific surface area value is 2.9 m 2 / g, change rate of crystallite diameter (150 ° C. ⁇ 30 minutes) is 118%, The rate of change (210 ° C. ⁇ 30 minutes) was 145%.
  • Example 5-1 Production of conductive paste> Diethylene glycol monoethyl such that 11.0 parts by weight of the polyester resin and 1.4 parts by weight of the curing agent with respect to 100 parts by weight of the silver fine particles of Example 4-1 and the content of the silver fine particles in the conductive paste is 70 wt%. Ether is added and premixed using a rotating / revolving mixer “Awatori Nertaro ARE-310” (registered trademark, manufactured by Sinky Corporation), and then uniformly mixed and dispersed using three rolls. Conductive paste was obtained.
  • the conductive paste obtained above was applied onto a polyimide film having a thickness of 50 ⁇ m and heated at 120 ° C., 210 ° C. and 300 ° C. for 30 minutes, respectively, to obtain a conductive coating film.
  • the specific resistance when the obtained conductive coating film is heat-treated at 120 ° C. for 30 minutes is 1.5 ⁇ 10 ⁇ 5 ⁇ ⁇ cm, and the specific resistance when heat-treated at 210 ° C. for 30 minutes is 6.8. ⁇ a 10 -6 ⁇ ⁇ cm, the specific resistance in the case of heat treatment at 300 ° C. 30 minutes was 3.1 ⁇ 10 -6 ⁇ ⁇ cm.
  • Silver fine particles and a conductive paste were produced according to Example 4-1 and Example 5-1. Various characteristics of each production condition and the obtained silver fine particle powder and electric paste are shown.
  • Example 4-6 Production of silver fine particles> After adding 475 g of silver nitrate and 3,808 g of ammonia water (25%) as a silver raw material to a 50 L reaction tower and mixing and stirring while cooling to 8 ° C. or lower, An aqueous complex solution was prepared. Separately, after adding 739 g of erythorbic acid (1.5 mol with respect to 1 mol of silver) and 3,530 g of pure water as a reducing agent to a 20 L plastic container, mixing and stirring while cooling to 9 ° C. or lower, A reducing agent-containing aqueous solution was prepared.
  • the reducing agent-containing aqueous solution was added to the silver salt complex aqueous solution with stirring while cooling the reaction system to 10 ° C. or less (addition time was 10 seconds or less). After completion of the addition, the mixture was stirred for 30 minutes and then allowed to stand for 30 minutes to precipitate the solid matter. After removing the supernatant by decantation, the filtrate was suction filtered using a filter paper, and then washed and filtered using pure water until the conductivity of the filtrate reached 15 ⁇ S / cm.
  • the obtained silver fine particle cake was redispersed in a methanol solution, the water on the surface of the silver fine particles was replaced with methanol, filtered, and dried in a vacuum dryer at 25 ° C. for 6 hours.
  • 4.2 g of a polymer compound “DISPERBYK-106” (trade name: manufactured by Big Chemie Japan Co., Ltd.) dispersed in a methanol solution was added to 300 g of the obtained silver fine particles (1 per silver fine particle). 4% by weight) and after stirring and mixing for 90 minutes, the methanol was distilled off.
  • the fine particles of Example 4-6 were obtained by pulverization with a jet pulverizer.
  • Examples 4-7 to 4-9 and Comparative Examples 4-3 to 4-4> Silver fine particles were obtained by variously changing the production conditions of the silver fine particles.
  • Example 4-10 Production of silver fine particles> After adding 160 g of silver nitrate and 800 mL of methanol to a 2 L beaker, 151.6 g of n-butylamine was added while cooling in a water bath, and then mixed and stirred while cooling to 18 ° C. or lower to prepare solution A. . Separately, 248.8 g of erythorbic acid was weighed into a 5 L beaker, dissolved by adding 1600 mL of water and stirred, and then mixed and stirred while cooling to 18 ° C. or lower by adding 800 mL of methanol to prepare solution B. .
  • the liquid B was stirred and the reaction system was cooled to 20 ° C. or lower, and the liquid A was added dropwise to the liquid B over 1 hour and 20 minutes. After the completion of dropping, the mixture was stirred for 14 hours and then allowed to stand for 30 minutes to precipitate a solid. After removing the supernatant liquid by decantation, suction filtration was performed using a filter paper, followed by washing and filtration using methanol and pure water.
  • the obtained silver fine particles were dried in a vacuum dryer for 30 minutes for 6 hours, and then the polymer compound “DISPERBYK-106” (trade name: dispersed in a methanol solution with respect to 24 g of the obtained silver fine particles). 0.48 g (manufactured by Big Chemie Japan Co., Ltd.) was added (2.0% by weight based on silver fine particles), and after stirring and mixing for 90 minutes, methanol was distilled off. Next, after drying at 25 ° C. for 6 hours in a vacuum dryer, the fine particles of Example 4-10 were obtained by pulverization with a jet pulverizer.
  • Table 7 shows the production conditions at this time, and Table 9 shows the characteristics of the obtained silver fine particles.
  • Table 10 shows the production conditions and various characteristics of the obtained conductive coating film.
  • the silver fine particles according to the present invention have a crystallite diameter ratio [crystallite diameter D X (111) / crystallite diameter D X (200)] of 1.40 and Miller index (111) by X-ray diffraction of 1.40. Because of the above, it is suitable as a raw material for conductive paste and the like that can be fired at a low temperature.

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Abstract

L'invention concerne de fines particules d'argent convenant en tant que matériau de départ pour par exemple une pâte conductrice pouvant être cuite à basse température, une pâte conductrice contenant lesdites fines particules d'argent, un film conducteur et un dispositif électronique. Les fines particules d'argent selon l'invention sont caractérisées en ce qu'elles présentent un rapport entre le diamètre cristallin à un indice de Miller en diffractométrie de rayons X de (111) et le diamètre cristallin à un indice de Miller en diffractométrie de rayons X de (200) [diamètre cristallin DX (111)/diamètre cristallin DX (200)] de 1/40.
PCT/JP2012/068939 2011-07-29 2012-07-26 Fines particules d'argent, pâte conductrice contenant de fines particules d'argent, film conducteur et dispositif électronique WO2013018645A1 (fr)

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US10639713B2 (en) 2014-03-05 2020-05-05 Sekisui Chemical Co., Ltd. Conductive filler, method for manufacturing conductive filler, and conductive paste

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