JP5985216B2 - Silver powder - Google Patents
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- JP5985216B2 JP5985216B2 JP2012054119A JP2012054119A JP5985216B2 JP 5985216 B2 JP5985216 B2 JP 5985216B2 JP 2012054119 A JP2012054119 A JP 2012054119A JP 2012054119 A JP2012054119 A JP 2012054119A JP 5985216 B2 JP5985216 B2 JP 5985216B2
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims description 148
- 238000010191 image analysis Methods 0.000 claims description 11
- 238000001000 micrograph Methods 0.000 claims description 7
- 238000005259 measurement Methods 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 2
- 238000000691 measurement method Methods 0.000 claims description 2
- 230000000930 thermomechanical effect Effects 0.000 claims description 2
- 239000002245 particle Substances 0.000 description 71
- 229910052709 silver Inorganic materials 0.000 description 65
- 239000004332 silver Substances 0.000 description 65
- 239000007864 aqueous solution Substances 0.000 description 57
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 50
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 35
- 229910001961 silver nitrate Inorganic materials 0.000 description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 25
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 21
- 239000001301 oxygen Substances 0.000 description 21
- 229910052760 oxygen Inorganic materials 0.000 description 21
- 238000003756 stirring Methods 0.000 description 21
- 238000000034 method Methods 0.000 description 19
- 239000000843 powder Substances 0.000 description 14
- 239000003638 chemical reducing agent Substances 0.000 description 12
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical class [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 11
- 235000011114 ammonium hydroxide Nutrition 0.000 description 11
- 239000002244 precipitate Substances 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- 238000009826 distribution Methods 0.000 description 10
- 239000000706 filtrate Substances 0.000 description 10
- 239000011347 resin Substances 0.000 description 10
- 229920005989 resin Polymers 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 239000004020 conductor Substances 0.000 description 8
- 239000002270 dispersing agent Substances 0.000 description 8
- 239000012798 spherical particle Substances 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 7
- 150000001412 amines Chemical class 0.000 description 6
- 230000001186 cumulative effect Effects 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- -1 alkanolamine Substances 0.000 description 5
- 239000011231 conductive filler Substances 0.000 description 5
- 235000014113 dietary fatty acids Nutrition 0.000 description 5
- 229930195729 fatty acid Natural products 0.000 description 5
- 239000000194 fatty acid Substances 0.000 description 5
- 239000010419 fine particle Substances 0.000 description 5
- 238000006722 reduction reaction Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000011164 primary particle Substances 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 3
- 239000010946 fine silver Substances 0.000 description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical class CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- 108010010803 Gelatin Proteins 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 239000011362 coarse particle Substances 0.000 description 2
- 239000008139 complexing agent Substances 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 description 2
- 229920000159 gelatin Polymers 0.000 description 2
- 239000008273 gelatin Substances 0.000 description 2
- 235000019322 gelatine Nutrition 0.000 description 2
- 235000011852 gelatine desserts Nutrition 0.000 description 2
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000004280 Sodium formate Substances 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 description 1
- VZTDIZULWFCMLS-UHFFFAOYSA-N ammonium formate Chemical compound [NH4+].[O-]C=O VZTDIZULWFCMLS-UHFFFAOYSA-N 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229940101006 anhydrous sodium sulfite Drugs 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- RJTANRZEWTUVMA-UHFFFAOYSA-N boron;n-methylmethanamine Chemical compound [B].CNC RJTANRZEWTUVMA-UHFFFAOYSA-N 0.000 description 1
- 239000005388 borosilicate glass Substances 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000012461 cellulose resin Substances 0.000 description 1
- 239000003985 ceramic capacitor Substances 0.000 description 1
- 239000013522 chelant Chemical class 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229960004279 formaldehyde Drugs 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 229940074391 gallic acid Drugs 0.000 description 1
- 235000004515 gallic acid Nutrition 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 229960001031 glucose Drugs 0.000 description 1
- 229940015043 glyoxal Drugs 0.000 description 1
- 229960004337 hydroquinone Drugs 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000007561 laser diffraction method Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000010956 nickel silver Substances 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 229940079877 pyrogallol Drugs 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001603 reducing effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 description 1
- 235000019254 sodium formate Nutrition 0.000 description 1
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 1
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 1
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 229940116411 terpineol Drugs 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- ZFZQOKHLXAVJIF-UHFFFAOYSA-N zinc;boric acid;dihydroxy(dioxido)silane Chemical compound [Zn+2].OB(O)O.O[Si](O)([O-])[O-] ZFZQOKHLXAVJIF-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- B22F1/052—Metallic powder characterised by the size or surface area of the particles characterised by a mixture of particles of different sizes or by the particle size distribution
-
- 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
Description
本発明は、焼結型導電性ペーストに好適に用いることができる銀粉に関する。 The present invention relates to a silver powder that can be suitably used for a sintered conductive paste.
導電性ペーストは、樹脂系バインダーと溶媒からなるビヒクル中に導電フィラーを分散させた流動性組成物であり、電気回路の形成や、セラミックコンデンサの外部電極の形成などに広く用いられている。この種の導電性ペーストには、樹脂の硬化によって導電性フィラーが圧着され導通を確保する樹脂硬化型と、高温焼結によって有機成分が揮発し導電性フィラーが焼結して導通を確保する焼結型とがある。 The conductive paste is a fluid composition in which a conductive filler is dispersed in a vehicle composed of a resin binder and a solvent, and is widely used for forming an electric circuit, an external electrode of a ceramic capacitor, and the like. This type of conductive paste includes a resin-curing type in which conductive fillers are pressure-bonded by hardening of the resin to ensure conduction, and a sintered type in which organic components are volatilized by high-temperature sintering and the conductive filler is sintered to ensure conduction. There is a type.
このうちの焼結型導電性ペーストは、一般に導電フィラー(金属粉末)とガラスフリットとを有機ビヒクル中に分散させてなるペースト状組成物であり、400〜800℃にて焼結することにより、有機ビヒクルが揮発し、さらに導電フィラーが焼結することによって導通性を確保するものである。この際、ガラスフリットは、この導電膜を基板に接着させる作用を有し、有機ビヒクルは、金属粉末およびガラスフリットを印刷可能にするための有機液体媒体として作用する。 Of these, the sintered conductive paste is a paste-like composition in which a conductive filler (metal powder) and glass frit are generally dispersed in an organic vehicle. By sintering at 400 to 800 ° C., The organic vehicle volatilizes and the conductive filler is sintered to ensure conductivity. At this time, the glass frit has a function of adhering the conductive film to the substrate, and the organic vehicle functions as an organic liquid medium for enabling printing of the metal powder and the glass frit.
このような焼結型導電性ペーストに用いる銀粉については、従来、電極や回路のファインライン化に対応すべく、微粒で且つシャープな粒度分布を有する銀粉が一般的に求められるため、それに対応した新たな技術が提案されている。
また、この種の銀粉には、乾式法で作製された乾式銀粉と湿式法で作製された湿式銀粉とがあるが、湿式銀粉は、小さな結晶が集まって一つの粒子を形成するため、乾式銀粉に比べて、焼成温度が低いという特徴がある。
For silver powder used in such a sintered conductive paste, conventionally, silver powder having a fine particle size and sharp particle size distribution is generally required in order to cope with fine lines of electrodes and circuits. New technologies have been proposed.
In addition, this type of silver powder includes a dry silver powder produced by a dry method and a wet silver powder produced by a wet method, but the wet silver powder is a dry silver powder because small crystals gather to form one particle. Compared to the above, the firing temperature is low.
そこで湿式銀粉に関し、従来、例えば特許文献1において、微粒の銀粉であって、しかも粉粒の凝集の少ない単分散により近い分散性を備える微粒銀粉として、走査型電子顕微鏡像の画像解析により得られる一次粒子の平均粒径DIAが0.6μm以下であり、前記一次粒子の平均粒径DIAと、レーザー回折散乱式粒度分布測定法による平均粒径D50とを用いてD50/DIAで表される凝集度が1.5以下であり、結晶子径が10nm以下であり、有機不純物含有量が炭素量換算で0.25wt%以下である微粒銀粉が提案されている。 Thus, regarding wet silver powder, conventionally, for example, in Patent Document 1, it is obtained by image analysis of a scanning electron microscopic image as fine silver powder, which is fine silver powder having dispersibility close to monodispersion with little aggregation of powder particles. The average particle diameter D IA of the primary particles is 0.6 μm or less, and the average particle diameter D IA of the primary particles and the average particle diameter D 50 by the laser diffraction scattering type particle size distribution measurement method are used to obtain D 50 / D IA A fine silver powder having a cohesion degree of 1.5 or less, a crystallite diameter of 10 nm or less, and an organic impurity content of 0.25 wt% or less in terms of carbon amount has been proposed.
また、特許文献2には、平均粒径が0.1μm以上、1μm未満であり、粒度分布がシャープでかつ高分散性の球状銀粉として、レーザー回折法により測定した累積10質量%粒径をD10、累積50質量%粒径をD50、累積90質量%粒径をD90と表記し、走査型電子顕微鏡像の画像解析から得られる一次粒子の平均粒径をDSEMと表記したとき、D50が0.1μm以上、1μm未満、且つ、D50/DSEMの値が1.3以下、且つ、(D90−D10)/D50の値が0.8以下であることを特徴とする球状銀粉が提案されている。 Further, Patent Document 2 discloses a cumulative 10% by mass particle size measured by laser diffraction method as a spherical silver powder having an average particle size of 0.1 μm or more and less than 1 μm, sharp particle size distribution and high dispersibility. When the cumulative 50 mass% particle diameter is expressed as D50, the cumulative 90 mass% particle diameter is expressed as D90, and the average particle diameter of the primary particles obtained from the image analysis of the scanning electron microscope image is expressed as DSEM, D50 is 0.00. There has been proposed a spherical silver powder characterized by having a value of 1 μm or more and less than 1 μm, a D50 / DSEM value of 1.3 or less, and a (D90-D10) / D50 value of 0.8 or less.
導電性ペーストを用いて電極や回路などの焼結導体を形成する際、均質で且つ、電気抵抗がより一層低い焼結導体を形成することは重要な課題の一つであり、そのための手段として、銀ペースト中の銀濃度を高くする方法が考えられる。
そこで本発明は、銀ペースト中の銀濃度を高くすることができ、均質で且つ、電気抵抗がより一層低い焼結導体を形成することができる、新たな銀粉を提供せんとするものである。
When forming sintered conductors such as electrodes and circuits using conductive paste, it is one of the important issues to form a sintered conductor that is homogeneous and has a lower electrical resistance. A method of increasing the silver concentration in the silver paste can be considered.
Therefore, the present invention is to provide a new silver powder that can increase the silver concentration in the silver paste, can form a sintered conductor that is homogeneous and has a lower electrical resistance.
本発明は、走査型電子顕微鏡像(SEM)の画像解析により得られるD50(「SEMD50」と称する)が2.50μm〜7.50μmであり、走査型電子顕微鏡像(SEM)の画像解析により得られるD10(「SEMD10」と称する)、D50(「SEMD50」と称する)及びD90(「SEMD90」と称する)の関係が、関係式:(SEMD90―SEMD10)/SEMD50≦0.50で示されることを特徴とする銀粉を提案する。 In the present invention, D50 (referred to as “ SEM D50”) obtained by image analysis of a scanning electron microscope image (SEM) is 2.50 μm to 7.50 μm, and image analysis of a scanning electron microscope image (SEM) The relationship between the obtained D10 (referred to as “ SEM D10”), D50 (referred to as “ SEM D50”) and D90 (referred to as “ SEM D90”) is the relational expression: ( SEM D90- SEM D10) / SEM D50 ≦ 0 A silver powder characterized by .50 is proposed.
本発明が提案する銀粉は、銀ペースト中の銀濃度を高くすることができ、均質で且つ、電気抵抗がより一層低い焼結導体を形成することができる。
従来の銀粉粒子は、微粒子を多く含むため、総じて比表面積が大きく、銀ペーストを調製する際には多量の樹脂が必要となり、そのため、ペースト中の銀濃度を高めることが難しく、その結果として焼結導体の電気抵抗が高くなってしまっていた。これに対し、本発明が提案する銀粉は、比較的大粒径でありながら、粒径が揃っているため、銀ペースト中の銀濃度を高くすることができ、均質で且つ、電気抵抗がより一層低い焼結導体を形成することができる。
The silver powder proposed by the present invention can increase the silver concentration in the silver paste, and can form a sintered conductor that is homogeneous and has an even lower electrical resistance.
Since conventional silver powder particles contain a large amount of fine particles, the specific surface area is generally large, and a large amount of resin is required when preparing a silver paste. Therefore, it is difficult to increase the silver concentration in the paste, and as a result The electrical resistance of the conductor was high. In contrast, the silver powder proposed by the present invention has a relatively large particle size and a uniform particle size, so that the silver concentration in the silver paste can be increased, and the electrical resistance is more uniform. Lower sintered conductors can be formed.
次に、実施の形態例に基づいて本発明を説明するが、本発明が次に説明する実施形態に限定されるものではない。 Next, the present invention will be described based on exemplary embodiments, but the present invention is not limited to the embodiments described below.
<本銀粉>
本実施形態に係る銀粉(以下、「本銀粉」と称する)は、査型電子顕微鏡像(SEM)の画像解析により得られるD50(「SEMD50」と称する)が2.50μm〜7.50μmであり、走査型電子顕微鏡像(SEM)の画像解析により得られるD10(「SEMD10」と称する)、D50(「SEMD50」と称する)及びD90(「SEMD90」と称する)の関係が、関係式:(SEMD90―SEMD10)/SEMD50≦0.50で示されることを特徴とする銀粉である。
以下、本銀粉の特徴について説明する。
<Silver powder>
The silver powder (hereinafter referred to as “main silver powder”) according to the present embodiment has a D50 (referred to as “ SEM D50”) obtained by image analysis of a scanning electron microscope image (SEM) of 2.50 μm to 7.50 μm. Yes, the relationship between D10 (referred to as “ SEM D10”), D50 (referred to as “ SEM D50”) and D90 (referred to as “ SEM D90”) obtained by image analysis of a scanning electron microscope image (SEM) Silver powder characterized by the formula: ( SEM D90- SEM D10) / SEM D50 ≦ 0.50.
Hereinafter, features of the present silver powder will be described.
(湿式銀粉)
本銀粉は、湿式法で作製される湿式銀粉、乾式法で作製される銀粉のいずれも包含する。中でも、湿式銀粉であるのが好ましい。
湿式銀粉の特徴は、小さな結晶子が集まって一つの粒子を形成するため、乾式法で作製される銀粉に比べて、TMA測定における500℃での収縮率が大きいという特徴がある。本銀粉が湿式銀粉であれば、TMA測定における500℃での収縮は1.0〜23.0%、中でも3.0%以上或いは23.0%以下となり、その中でも好ましくは5.0%以上或いは23.0%以下となる。
(Wet silver powder)
The present silver powder includes both wet silver powder produced by a wet method and silver powder produced by a dry method. Among these, wet silver powder is preferable.
A characteristic of wet silver powder is that small crystallites gather to form one particle, and therefore, the shrinkage rate at 500 ° C. in TMA measurement is larger than that of silver powder produced by a dry method. If the present silver powder is a wet silver powder, the shrinkage at 500 ° C. in the TMA measurement is 1.0 to 23.0%, particularly 3.0% or more or 23.0% or less, and preferably 5.0% or more. Or it becomes 23.0% or less.
このとき、上記のTMA測定における収縮率は次のように測定することができる。
銀粉(サンプル)0.2gを用い、493kgの加重をかけてφ3.8mmの円柱状に成形した。この成形体の縦方向の線収縮率(%)を、イコーインスツルメンツ社製の熱機械分析装置(TMA)(EXSTAR6000TMA/SS6200)を用い、98mNの加重をかけながらAir雰囲気中20℃/分の昇温速度で測定し、500℃における熱収縮率(%)を求めることができる。
At this time, the shrinkage rate in the above TMA measurement can be measured as follows.
Using 0.2 g of silver powder (sample), a weight of 493 kg was applied and molded into a cylindrical shape of φ3.8 mm. Using a thermomechanical analyzer (TMA) (EXSTAR6000TMA / SS6200) manufactured by Iko Instruments Co., Ltd., the linear shrinkage rate (%) in the longitudinal direction of this molded body was increased by 20 ° C./min in an Air atmosphere while applying a load of 98 mN. The heat shrinkage rate (%) at 500 ° C. can be determined by measuring at a temperature rate.
また、湿式法によれば、真球状或いは略真球状の粒子であって、且つ大粒径のものを作製することができる。乾式法であっても、アトマイズ法或いはPVD法によって球状の粒子を作製することは可能であるが、アトマイズ法では真球粒子を作製することは困難であるし、PVD法では、真球が得られても、本発明が規定するほど大きな粒子を作製することは困難である。 In addition, according to the wet method, spherical particles or substantially spherical particles having a large particle diameter can be produced. Even with the dry method, it is possible to produce spherical particles by the atomizing method or the PVD method, but it is difficult to produce true spherical particles by the atomizing method, and a true sphere is obtained by the PVD method. Even so, it is difficult to produce particles as large as the present invention defines.
(D50)
本銀粉においては、走査型電子顕微鏡(SEM)像の画像解析により得られるD50(「SEMD50」と称する)が2.50μm〜7.50μmであることが重要である。
本銀粉のSEMD50が2.50μm以上であれば、ペースト調製時に樹脂の量を減らすことができ、その結果として形成した焼結導体の電気抵抗を低くすることができる。また、SEMD50が7.50μm以下であれば比較的安定的に製造できる。
よって、かかる観点から、本銀粉のSEMD50は、特に3.00μm以上、或いは6.50μm以下、中でも3.00μm以上、或いは、5.50μm以下であるのがより一層好ましい。
(D50)
In the present silver powder, it is important that D50 (referred to as “ SEM D50”) obtained by image analysis of a scanning electron microscope (SEM) image is 2.50 μm to 7.50 μm.
If the SEM D50 of the present silver powder is 2.50 μm or more, the amount of the resin can be reduced at the time of preparing the paste, and as a result, the electric resistance of the formed sintered conductor can be lowered. Moreover, if SEM D50 is 7.50 micrometers or less, it can manufacture comparatively stably.
Therefore, from this viewpoint, the SEM D50 of the present silver powder is more preferably 3.00 μm or more, or 6.50 μm or less, and particularly preferably 3.00 μm or more, or 5.50 μm or less.
(粒度分布)
本銀粉においては、走査型電子顕微鏡(SEM)像の画像解析により得られるD10(「SEMD10」と称する)、D50(「SEMD50」と称する)及びD90(「SEMD90」と称する)の関係が、関係式:(SEMD90―SEMD10)/SEMD50≦0.50で示されることが重要である。
(Particle size distribution)
In the present silver powder, D10 (referred to as “ SEM D10”), D50 (referred to as “ SEM D50”), and D90 (referred to as “ SEM D90”) obtained by image analysis of a scanning electron microscope (SEM) image. However, it is important that the relationship is expressed by the relational expression: ( SEM D90− SEM D10) / SEM D50 ≦ 0.50
ここで、D10は、走査型電子顕微鏡(SEM)像の画像解析により得られる粒度分布における個数基準累積度数10%の粒子径の意味であり、D50は、当該個数基準累積度数50%の粒子径の意味であり、D90は、当該個数基準累積度数90%の粒子径の意味である。 Here, D10 means the particle size of a number-based cumulative frequency of 10% in the particle size distribution obtained by image analysis of a scanning electron microscope (SEM) image, and D50 is the particle size of the number-based cumulative frequency of 50%. D90 means the particle size of the number-based cumulative frequency of 90%.
(SEMD90―SEMD10)/SEMD50の値が0.50以下であれば、粒度分布が揃っており、均質な導電性ペーストを形成することができるばかりか、ある温度域で短時間のうちに焼結させることができる。かかる観点から、(SEMD90―SEMD10)/SEMD50の値は0.20以上或いは0.44以下であるのが好ましく、中でも0.20以上或いは0.40以下であるのがより一層好ましい。 If the value of ( SEM D90- SEM D10) / SEM D50 is 0.50 or less, the particle size distribution is uniform and not only can a homogeneous conductive paste be formed, but also in a short time at a certain temperature range. Can be sintered. From this viewpoint, the value of ( SEM D90- SEM D10) / SEM D50 is preferably 0.20 or more or 0.44 or less, and more preferably 0.20 or more or 0.40 or less.
ただし、微粒子や粗粒子が若干含まれていても、効果に影響は少ないため、おおまかに見て粒度が揃っていればよい。その意味で(SEMD90―SEMD10)/SEMD50の値が0.50以下であれば、微粒子や粗粒子が含まれていてもよい。
また、(SEMD90―SEMD10)/SEMD50の分布が、一つの頂点と両側になめらかな裾野を有する単峰性ピークを示すものであり、分級によって区切られる分布とは区別されるものである。
However, even if some fine particles and coarse particles are included, the effect is small, and it is sufficient that the particle sizes are roughly uniform. In that sense, if the value of ( SEM D90- SEM D10) / SEM D50 is 0.50 or less, fine particles and coarse particles may be included.
In addition, the distribution of ( SEM D90- SEM D10) / SEM D50 shows a unimodal peak having one apex and a smooth skirt on both sides, and is distinguished from the distribution divided by classification. .
<製法>
次に、本銀粉の好ましい製造方法として、湿式法による具体的な製造方法について説明する。但し、上述のように湿式法に限定するものではない。
<Production method>
Next, a specific manufacturing method by a wet method will be described as a preferable manufacturing method of the present silver powder. However, it is not limited to the wet method as described above.
従来の湿式還元法で大粒径の銀粉を製造しようとすると、還元反応をゆっくりと進行させ、粒子を成長させる過程が必要であった。しかし、そのようにすると、小粒径或いは小粒径の凝集体が混在するようになるためシャープな粒度分布を得ることは困難であった。また、アトマイズ法によって大粒径を製造することは可能であるが、粒子が安定過ぎる為に、焼結温度が高くなり、焼結型導電性ペーストに用いる銀粉としては不向きとなる。さらにまた、分級によって大粒径且つシャープな粒度分布を得ることも可能であるが、生産性が問題であった。
そこで、本発明は、還元反応に用いる還元剤溶液の溶存酸素を高めて、銀原料溶液、還元剤溶液およびその他添加剤を静止した状態で反応させることで、大粒径であり、且つ粒径が揃っている銀粉を得ることに成功した。すなわち、還元剤溶液中の溶存酸素が少ないと、すぐに還元反応が始まって微粒子ができてしまうが、溶存酸素が多ければ、先ず溶存酸素が還元反応するので、銀が反応して還元析出するまでの時間を稼ぐことができる。よって、この間に、還元剤溶液の液組成が均質で落ち着いた状態になり、その結果、還元析出される粒度を揃えることができ、一次粒子の粒径が大きく且つ粒径が揃った湿式銀粉を得ることができる。
In order to produce silver powder having a large particle size by the conventional wet reduction method, a process of slowly proceeding the reduction reaction and growing the particles is necessary. However, in such a case, it is difficult to obtain a sharp particle size distribution because small particles or aggregates with small particles are mixed. Moreover, although it is possible to manufacture a large particle size by the atomizing method, since the particles are too stable, the sintering temperature becomes high, making it unsuitable as a silver powder for use in a sintered conductive paste. Furthermore, it is possible to obtain a large particle size and a sharp particle size distribution by classification, but productivity is a problem.
Therefore, the present invention increases the dissolved oxygen in the reducing agent solution used for the reduction reaction, and reacts the silver raw material solution, the reducing agent solution and other additives in a stationary state, thereby increasing the particle size. We succeeded in obtaining silver powder with That is, if the dissolved oxygen in the reducing agent solution is small, the reduction reaction starts immediately and fine particles are formed. However, if there is a large amount of dissolved oxygen, the dissolved oxygen first undergoes a reduction reaction, so that silver reacts to reduce and precipitate. You can earn time. Therefore, during this time, the liquid composition of the reducing agent solution is in a homogeneous and calm state, and as a result, the particle size to be reduced and precipitated can be made uniform, and the wet silver powder having a large primary particle size and a uniform particle size can be obtained. Can be obtained.
ここで、本銀粉の製造方法の具体的な一例について説明する。
先ず、硝酸銀などの銀水溶液に錯化剤を加え、必要に応じてステアリン酸NaやKなどのステアリン酸塩を加えて撹拌した後、溶存酸素量を高めた還元剤溶液を添加し、次いで必要に応じて分散剤を添加して撹拌することなく反応させて銀粒子を還元析出させ、その後、ろ過、洗浄、乾燥などの工程を経て、本銀粉を得ることができる。
Here, the specific example of the manufacturing method of this silver powder is demonstrated.
First, a complexing agent is added to a silver aqueous solution such as silver nitrate, and a stearic acid salt such as Na or K stearate is added and stirred as necessary. Then, a reducing agent solution with an increased amount of dissolved oxygen is added, and then necessary. Accordingly, the silver powder can be reduced and precipitated by adding a dispersant and reacting without stirring, followed by filtration, washing, drying, and the like to obtain the present silver powder.
ここで、還元剤溶液は、純水に還元剤(ヒドラジン)を添加して調製し、その際に、純水に還元剤(ヒドラジン)を添加してから、銀水溶液に添加するまでの時間によって、還元剤溶液における溶存酸素量の調整を図ることができる。つまり、純水に還元剤(ヒドラジン)を添加すると、もともと純水に含まれている溶存酸素が還元剤(ヒドラジン)による還元作用によって消費されて経過時間とともに少なくなるため、純水に還元剤(ヒドラジン)を添加した後、できるだけ短時間のうちに銀溶液に添加するのが好ましい。
ただし、純水をバブリングするなど、溶液中の溶存酸素量を増加させるようにしてもよい。
Here, the reducing agent solution is prepared by adding a reducing agent (hydrazine) to pure water. At that time, depending on the time from adding the reducing agent (hydrazine) to pure water until adding to the silver aqueous solution. The amount of dissolved oxygen in the reducing agent solution can be adjusted. That is, when a reducing agent (hydrazine) is added to pure water, the dissolved oxygen originally contained in the pure water is consumed by the reducing action of the reducing agent (hydrazine) and decreases with time. It is preferable to add to the silver solution in as short a time as possible after adding hydrazine).
However, the amount of dissolved oxygen in the solution may be increased by bubbling pure water.
上記の製法において、硝酸銀などの銀水溶液は、硝酸銀、銀塩錯体、及び銀中間体のいずれかを含有する水溶液、又はスラリーを使用することができる。
また、錯化剤としては、例えばアンモニア水、アンモニウム塩、キレート化合物等を挙げることができる。
還元剤としては、アスコルビン酸、亜硫酸塩、アルカノールアミン、過酸化水素水、ギ酸、ギ酸アンモニウム、ギ酸ナトリウム、グリオキサール、酒石酸、次亜燐酸ナトリウム、水素化ホウ素金属塩、ジメチルアミンボラン、ヒドラジン、ヒドラジン化合物、ヒドロキノン、ピロガロール、ぶどう糖、没食子酸、ホルマリン、無水亜硫酸ナトリウム、ロンガリットなどを含む水溶液を挙げることができる。
分散剤としては、脂肪酸、脂肪酸塩、界面活性剤、有機金属、キレート剤、保護コロイド等を挙げることができる。
In the above production method, an aqueous solution containing silver nitrate, a silver salt complex, and a silver intermediate or a slurry can be used as the aqueous silver solution such as silver nitrate.
Examples of complexing agents include ammonia water, ammonium salts, chelate compounds and the like.
As reducing agents, ascorbic acid, sulfite, alkanolamine, hydrogen peroxide, formic acid, ammonium formate, sodium formate, glyoxal, tartaric acid, sodium hypophosphite, borohydride metal salt, dimethylamine borane, hydrazine, hydrazine compound And aqueous solutions containing hydroquinone, pyrogallol, glucose, gallic acid, formalin, anhydrous sodium sulfite, Rongalite and the like.
Examples of the dispersant include fatty acids, fatty acid salts, surfactants, organic metals, chelating agents, protective colloids and the like.
(形状加工)
本銀粉は、そのまま利用することも可能であるが、本銀粉を形状加工処理した上で、利用することもできる。
例えば、球状粒子粉末(:80%以上が球状粒子からなる粉末)を、機械的に形状加工して、フレーク状、鱗片状、平板状などの非球状粒子粉末(:80%以上が非球状粒子からなる粉末)に加工することができる。
より具体的には、ビーズミル、ボールミル、アトライター、振動ミルなどを用いて機械的に偏平化加工(圧伸延または展伸)することにより、フレーク状粒子粉末(:80%以上がフレーク状粒子からなる粉末)に形状加工することができる。この際、粒子同士の凝集や結合を防止しながら各粒子を独立した状態で加工するために、例えばステアリン酸などの脂肪酸や、界面活性剤などの助剤を添加するのが好ましい。
そして、このような形状加工処理した銀粉を利用することもできるし、また、形状加工しない元粉とこれとを混合して利用することもできる。
(Shape processing)
Although the present silver powder can be used as it is, it can also be used after the present silver powder has been processed into a shape.
For example, a spherical particle powder (powder consisting of 80% or more of spherical particles) is mechanically processed into non-spherical particle powders such as flakes, scales, and flat plates (: 80% or more of non-spherical particles) Powder).
More specifically, flaky particle powder (: 80% or more from flaky particles) is mechanically flattened (rolled or stretched) using a bead mill, ball mill, attritor, vibration mill or the like. Shape powder). At this time, in order to process each particle independently while preventing aggregation and bonding of the particles, it is preferable to add a fatty acid such as stearic acid or an auxiliary agent such as a surfactant.
And the silver powder which carried out such shape processing can also be utilized, and the original powder which is not shape-processed and this can also be mixed and utilized.
本銀粉は、粒径がきれいに揃っているため、粒径に適したメディアを効果的に選択できるため、フレーク粉としても、均質なフレーク粉粒子を得ることができる。
球形粉とフレーク粉の混合粉でもよい。
Since the present silver powder has a uniform particle size, a medium suitable for the particle size can be effectively selected, so that even flake powder can obtain uniform flake powder particles.
A mixed powder of spherical powder and flake powder may be used.
<用途>
本銀粉は、導電ペースト用、特に焼結型導電性ペースト用の銀粉として好適である。
<Application>
The silver powder is suitable as a silver powder for a conductive paste, particularly for a sintered conductive paste.
焼結型導電性ペーストは、例えば有機ビヒクル中に、本銀粉をガラスフリットと共に混合することで調製することができる。
この際、ガラスフリットとしては、例えば、鉛ボロシリケートガラスや、ジンクボロシリケート等の無鉛ガラスも挙げることができる。
また、樹脂バインダーとしては、例えば任意の樹脂バインダーを使用することができる。例えばエポキシ樹脂、ポリエステル樹脂、ケイ素樹脂、ユリア樹脂、アクリル樹脂、セルロース樹脂から選ばれる1種以上を含む組成を採用するのが望ましい。
The sintered conductive paste can be prepared, for example, by mixing the present silver powder together with glass frit in an organic vehicle.
In this case, examples of the glass frit include lead-free glass such as lead borosilicate glass and zinc borosilicate.
Moreover, as a resin binder, arbitrary resin binders can be used, for example. For example, it is desirable to employ a composition containing at least one selected from an epoxy resin, a polyester resin, a silicon resin, a urea resin, an acrylic resin, and a cellulose resin.
<語句の説明>
本明細書において「X〜Y」(X,Yは任意の数字)と表現する場合、特にことわらない限り「X以上Y以下」の意と共に、「好ましくはXより大きい」或いは「好ましくはYより小さい」の意も包含する。
また、「X以上」(Xは任意の数字)或いは「Y以下」(Yは任意の数字)と表現した場合、「Xより大きいことが好ましい」或いは「Y未満であることが好ましい」旨の意図も包含する。
<Explanation of words>
In the present specification, when expressed as “X to Y” (X and Y are arbitrary numbers), unless otherwise specified, “X is preferably greater than X” or “preferably Y”. It also includes the meaning of “smaller”.
In addition, when expressed as “X or more” (X is an arbitrary number) or “Y or less” (Y is an arbitrary number), it is “preferably greater than X” or “preferably less than Y”. Includes intentions.
以下、本発明を下記実施例及び比較例に基づいてさらに詳述する。
実施例および比較例で得られた銀粉に関して、以下に示す方法で諸特性を評価した。
Hereinafter, the present invention will be further described in detail based on the following examples and comparative examples.
With respect to the silver powder obtained in Examples and Comparative Examples, various characteristics were evaluated by the following methods.
(1)SEMD10、SEMD50、SEMD90
走査型電子顕微鏡(SEM)(PHILIPS社製 XL30)を用いて1000〜3000倍にて撮影した任意の3視野の走査型電子顕微鏡(SEM)像を、BMPファイルに変換し、旭エンジニアリング株式会社製のIP−1000PCの統合アプリケーションであるA像くんで取り込み、円度しきい値50、重なり度30、標本数150〜350として円形粒子解析を行ない、SEMD10、SEMD50、SEMD90を手動補正をかけることなく計測した。
(1) SEM D10, SEM D50, SEM D90
An arbitrary three field scanning electron microscope (SEM) image taken at 1000 to 3000 times using a scanning electron microscope (SEM) (XL30 manufactured by PHILIPS) is converted into a BMP file and manufactured by Asahi Engineering Co., Ltd. A-image PC, which is an integrated application of IP-1000PC, and circular particle analysis was performed with circularity threshold 50, overlap 30 and sample number 150-350, and SEM D10, SEM D50, SEM D90 were manually corrected Measured without applying.
(2)溶存酸素
HORIBA製作所製のDO(溶存酸素)計(OM−51)を用いて、ヒドラジン水溶液中の溶存酸素濃度を測定した。
(2) Dissolved oxygen The dissolved oxygen concentration in the hydrazine aqueous solution was measured using a DO (dissolved oxygen) meter (OM-51) manufactured by HORIBA.
(3)均質性評価
銀粉3.5gに、エチルセルロース(100cp)を5%含有したテルピネオールを少量ずつ加えながらヘラで混合していき、樹脂が一様になじんだ時点での樹脂添加量(Xg)を測定した。ペースト中の銀濃度を次の式で求め、95%以上を均質性が高いと判断した。
(3) Homogeneity evaluation Addition of terpineol containing 5% ethyl cellulose (100 cp) to 3.5 g of silver powder with a spatula while adding little by little, the resin addition amount (Xg) when the resin is evenly blended Was measured. The silver concentration in the paste was determined by the following formula, and 95% or more was judged to have high homogeneity.
(ペースト中の銀濃度(%))={(銀粉3.5g)/(銀粉3.5g+樹脂添加量Xg)}×100 (Silver concentration in paste (%)) = {(silver powder 3.5 g) / (silver powder 3.5 g + resin addition amount Xg)} × 100
<実施例1>
銀濃度400g/Lの硝酸銀水溶液50mLを純水1Lに溶解させて硝酸銀水溶液を調製し、濃度25質量%のアンモニア水60mLを添加して攪拌することにより、銀アンミン錯体水溶液を得た。
次いで、20〜30℃の銀アンミン錯体水溶液に、1%濃度のアミン系の分散剤(平均分子量10000)水溶液6mLを添加して攪拌し、溶存酸素濃度6.00〜8.00mg/Lに調整した濃度11.9g/Lのヒドラジン水溶液1Lを混合し、撹拌することなく反応させて銀粒子を還元析出させた。
次いで、この銀粒子をろ過し、ろ液の伝導率が40μS/cm以下となるまで水洗後、乾燥させることにより銀粉(サンプル)を得た。得られた銀粉粒子は略真球状であった。
<Example 1>
A silver nitrate aqueous solution was obtained by dissolving 50 mL of a silver nitrate aqueous solution having a silver concentration of 400 g / L in 1 L of pure water, adding 60 mL of ammonia water having a concentration of 25% by mass, and stirring.
Next, 6 mL of a 1% concentration amine-based dispersant (average molecular weight 10,000) aqueous solution is added to a 20-30 ° C. silver ammine complex aqueous solution and stirred to adjust the dissolved oxygen concentration to 6.00 to 8.00 mg / L. 1 L of a hydrazine aqueous solution having a concentration of 11.9 g / L was mixed and reacted without stirring to reduce and precipitate silver particles.
Then, the silver particles were filtered, washed with water until the filtrate had a conductivity of 40 μS / cm or less, and dried to obtain silver powder (sample). The obtained silver powder particles were substantially spherical.
<実施例2>
銀濃度400g/Lの硝酸銀水溶液50mLを純水1Lに溶解させて硝酸銀水溶液を調製し、濃度25質量%のアンモニア水60mLを添加して攪拌することにより、銀アンミン錯体水溶液を得た。
次いで、20〜30℃の銀アンミン錯体水溶液に、1%濃度のアミン系の分散剤(平均分子量10000)水溶液10mLを添加して攪拌し、溶存酸素濃度6.00〜8.00mg/Lに調整した濃度11.9g/Lのヒドラジン水溶液1Lを混合し、撹拌することなく反応させて銀粒子を還元析出させた。
次いで、この銀粒子をろ過し、ろ液の伝導率が40μS/cm以下となるまで水洗後、乾燥させることにより銀粉(サンプル)を得た。得られた銀粉粒子は略真球状であった。
<Example 2>
A silver nitrate aqueous solution was obtained by dissolving 50 mL of a silver nitrate aqueous solution having a silver concentration of 400 g / L in 1 L of pure water, adding 60 mL of ammonia water having a concentration of 25% by mass, and stirring.
Next, 10 mL of a 1% concentration amine-based dispersant (average molecular weight 10,000) aqueous solution is added to a 20-30 ° C. silver ammine complex aqueous solution and stirred to adjust the dissolved oxygen concentration to 6.00 to 8.00 mg / L. 1 L of a hydrazine aqueous solution having a concentration of 11.9 g / L was mixed and reacted without stirring to reduce and precipitate silver particles.
Then, the silver particles were filtered, washed with water until the filtrate had a conductivity of 40 μS / cm or less, and dried to obtain silver powder (sample). The obtained silver powder particles were substantially spherical.
<実施例3>
銀濃度400g/Lの硝酸銀水溶液50mLを純水1Lに溶解させて硝酸銀水溶液を調製し、濃度25質量%のアンモニア水60mLを添加して攪拌することにより、銀アンミン錯体水溶液を得た。
次いで、20℃の銀アンミン錯体水溶液に、溶存酸素濃度6.00〜8.00mg/Lに調整した、濃度11.9g/Lのヒドラジン水溶液1Lと濃度2.9g/Lの脂肪酸塩水溶液35mL(銀1molに対して1.76×10-3molに相当)の混合溶液を加えて、撹拌することなく反応させて銀粒子を還元析出させた。
次いで、この銀粒子をろ過し、ろ液の伝導率が40μS/cm以下となるまで水洗後、乾燥させることにより銀粉(サンプル)を得た。得られた銀粉粒子は略真球状であった。
<Example 3>
A silver nitrate aqueous solution was obtained by dissolving 50 mL of a silver nitrate aqueous solution having a silver concentration of 400 g / L in 1 L of pure water, adding 60 mL of ammonia water having a concentration of 25% by mass, and stirring.
Next, in a silver ammine complex aqueous solution at 20 ° C., 1 L of a hydrazine aqueous solution having a concentration of 11.9 g / L and 35 mL of a fatty acid salt aqueous solution having a concentration of 2.9 g / L adjusted to a dissolved oxygen concentration of 6.00 to 8.00 mg / L ( A mixed solution of 1.76 × 10 −3 mol corresponding to 1 mol of silver) was added and reacted without stirring to reduce and precipitate silver particles.
Then, the silver particles were filtered, washed with water until the filtrate had a conductivity of 40 μS / cm or less, and dried to obtain silver powder (sample). The obtained silver powder particles were substantially spherical.
<実施例4>
銀濃度400g/Lの硝酸銀水溶液50mLを純水1Lに溶解させて硝酸銀水溶液を調製し、濃度25質量%のアンモニア水50mLを添加して攪拌することにより、銀アンミン錯体水溶液を得た。次いで、20℃の銀アンミン錯体水溶液に、溶存酸素濃度6.00〜8.00mg/Lに調整した、濃度11.9g/Lのヒドラジン水溶液1Lと濃度5g/Lのゼラチン水溶液48mL(銀1molに対して1.29gに相当)の混合溶液を加えて、撹拌することなく反応させて銀粒子を還元析出させた。
次いで、この銀粒子をろ過し、ろ液の伝導率が40μS/cm以下となるまで水洗後、乾燥させることにより銀粉(サンプル)を得た。得られた銀粉粒子は略真球状であった。
<Example 4>
A silver nitrate aqueous solution was obtained by dissolving 50 mL of a silver nitrate aqueous solution having a silver concentration of 400 g / L in 1 L of pure water to prepare a silver nitrate aqueous solution, adding 50 mL of ammonia water having a concentration of 25% by mass and stirring. Next, in a silver ammine complex aqueous solution at 20 ° C., 1 L of a hydrazine aqueous solution having a concentration of 11.9 g / L adjusted to a dissolved oxygen concentration of 6.00 to 8.00 mg / L and 48 mL of a gelatin aqueous solution having a concentration of 5 g / L (into 1 mol of silver). (Corresponding to 1.29 g), and the mixture was reacted without stirring to reduce and precipitate silver particles.
Then, the silver particles were filtered, washed with water until the filtrate had a conductivity of 40 μS / cm or less, and dried to obtain silver powder (sample). The obtained silver powder particles were substantially spherical.
<比較例1>
銀濃度400g/Lの硝酸銀水溶液50mLを純水1Lに溶解させて硝酸銀水溶液を調製し、濃度25質量%のアンモニア水60mLを添加して攪拌することにより、銀アンミン錯体水溶液を得た。
次いで、20〜30℃の銀アンミン錯体水溶液に、1%濃度のアミン系の分散剤(平均分子量10000)水溶液6mLを添加して攪拌し、溶存酸素濃度3.00〜5.00mg/Lに調整した濃度11.9g/Lのヒドラジン水溶液1Lを混合し、撹拌することなく反応させて銀粒子を還元析出させた。
次いで、この銀粒子をろ過し、ろ液の伝導率が40μS/cm以下となるまで水洗後、乾燥させることにより銀粉(サンプル)を得た。
<Comparative Example 1>
A silver nitrate aqueous solution was obtained by dissolving 50 mL of a silver nitrate aqueous solution having a silver concentration of 400 g / L in 1 L of pure water, adding 60 mL of ammonia water having a concentration of 25% by mass, and stirring.
Next, 6 mL of a 1% concentration amine-based dispersant (average molecular weight 10,000) aqueous solution is added to 20-30 ° C. silver ammine complex aqueous solution and stirred to adjust the dissolved oxygen concentration to 3.00-5.00 mg / L. 1 L of a hydrazine aqueous solution having a concentration of 11.9 g / L was mixed and reacted without stirring to reduce and precipitate silver particles.
Then, the silver particles were filtered, washed with water until the filtrate had a conductivity of 40 μS / cm or less, and dried to obtain silver powder (sample).
<比較例2>
銀濃度400g/Lの硝酸銀水溶液50mLを純水1Lに溶解させて硝酸銀水溶液を調製し、濃度25質量%のアンモニア水60mLを添加して攪拌することにより、銀アンミン錯体水溶液を得た。
次いで、20〜30℃の銀アンミン錯体水溶液に、1%濃度のアミン系の分散剤(平均分子量10000)水溶液6mLを添加して攪拌し、溶存酸素濃度0.20〜2.00mg/Lに調整した濃度11.9g/Lのヒドラジン水溶液1Lを混合し、撹拌することなく反応させて銀粒子を還元析出させた。
次いで、この銀粒子をろ過し、ろ液の伝導率が40μS/cm以下となるまで水洗後、乾燥させることにより銀粉(サンプル)を得た。
<Comparative example 2>
A silver nitrate aqueous solution was obtained by dissolving 50 mL of a silver nitrate aqueous solution having a silver concentration of 400 g / L in 1 L of pure water, adding 60 mL of ammonia water having a concentration of 25% by mass, and stirring.
Next, 6 mL of a 1% concentration amine-based dispersant (average molecular weight 10,000) aqueous solution is added to 20-30 ° C. silver ammine complex aqueous solution and stirred to adjust the dissolved oxygen concentration to 0.20-2.00 mg / L. 1 L of a hydrazine aqueous solution having a concentration of 11.9 g / L was mixed and reacted without stirring to reduce and precipitate silver particles.
Then, the silver particles were filtered, washed with water until the filtrate had a conductivity of 40 μS / cm or less, and dried to obtain silver powder (sample).
<比較例3>
銀濃度400g/Lの硝酸銀水溶液50mLを純水1Lに溶解させて硝酸銀水溶液を調製し、濃度25質量%のアンモニア水60mLを添加して攪拌することにより、銀アンミン錯体水溶液を得た。
次いで、20〜30℃の銀アンミン錯体水溶液に、1%濃度のアミン系の分散剤(平均分子量10000)水溶液10mLを添加して攪拌し、溶存酸素濃度3.00〜5.00mg/Lに調整した濃度11.9g/Lのヒドラジン水溶液1Lを混合し、撹拌することなく反応させて銀粒子を還元析出させた。
次いで、この銀粒子をろ過し、ろ液の伝導率が40μS/cm以下となるまで水洗後、乾燥させることにより銀粉(サンプル)を得た。
<Comparative Example 3>
A silver nitrate aqueous solution was obtained by dissolving 50 mL of a silver nitrate aqueous solution having a silver concentration of 400 g / L in 1 L of pure water, adding 60 mL of ammonia water having a concentration of 25% by mass, and stirring.
Next, 10 mL of a 1% concentration amine-based dispersant (average molecular weight 10,000) aqueous solution is added to 20-30 ° C. silver ammine complex aqueous solution and stirred to adjust the dissolved oxygen concentration to 3.00-5.00 mg / L. 1 L of a hydrazine aqueous solution having a concentration of 11.9 g / L was mixed and reacted without stirring to reduce and precipitate silver particles.
Then, the silver particles were filtered, washed with water until the filtrate had a conductivity of 40 μS / cm or less, and dried to obtain silver powder (sample).
<比較例4>
銀濃度400g/Lの硝酸銀水溶液50mLを純水1Lに溶解させて硝酸銀水溶液を調製し、濃度25質量%のアンモニア水60mLを添加して攪拌することにより、銀アンミン錯体水溶液を得た。
次いで、20〜30℃の銀アンミン錯体水溶液に、1%濃度のアミン系の分散剤(平均分子量10000)水溶液10mLを添加して攪拌し、溶存酸素濃度0.20〜2.00mg/Lに調整した濃度11.9g/Lのヒドラジン水溶液1Lを混合し、撹拌することなく反応させて銀粒子を還元析出させた。
次いで、この銀粒子をろ過し、ろ液の伝導率が40μS/cm以下となるまで水洗後、乾燥させることにより銀粉(サンプル)を得た。
<Comparative example 4>
A silver nitrate aqueous solution was obtained by dissolving 50 mL of a silver nitrate aqueous solution having a silver concentration of 400 g / L in 1 L of pure water, adding 60 mL of ammonia water having a concentration of 25% by mass, and stirring.
Next, 10 mL of a 1% concentration amine-based dispersant (average molecular weight 10,000) aqueous solution is added to a 20-30 ° C. silver ammine complex aqueous solution and stirred to adjust the dissolved oxygen concentration to 0.20-2.00 mg / L. 1 L of a hydrazine aqueous solution having a concentration of 11.9 g / L was mixed and reacted without stirring to reduce and precipitate silver particles.
Then, the silver particles were filtered, washed with water until the filtrate had a conductivity of 40 μS / cm or less, and dried to obtain silver powder (sample).
<比較例5>
銀濃度400g/Lの硝酸銀水溶液50mLを純水1Lに溶解させて硝酸銀水溶液を調製し、濃度25質量%のアンモニア水60mLを添加して攪拌することにより、銀アンミン錯体水溶液を得た。
次いで、20℃の銀アンミン錯体水溶液に、溶存酸素濃度0.20〜2.00mg/Lに調整した、濃度11.9g/Lのヒドラジン水溶液1Lと濃度2.9g/Lの脂肪酸塩水溶液35mL(銀1molに対して1.76×10-3molに相当)の混合溶液を加えて、撹拌することなく反応させて銀粒子を還元析出させた。
次いで、この銀粒子をろ過し、ろ液の伝導率が40μS/cm以下となるまで水洗後、乾燥させることにより銀粉(サンプル)を得た。
<Comparative Example 5>
A silver nitrate aqueous solution was obtained by dissolving 50 mL of a silver nitrate aqueous solution having a silver concentration of 400 g / L in 1 L of pure water, adding 60 mL of ammonia water having a concentration of 25% by mass, and stirring.
Next, in a silver ammine complex aqueous solution at 20 ° C., 1 L of a hydrazine aqueous solution having a concentration of 11.9 g / L and 35 mL of a fatty acid salt aqueous solution having a concentration of 2.9 g / L adjusted to a dissolved oxygen concentration of 0.20 to 2.00 mg / L ( A mixed solution of 1.76 × 10 −3 mol corresponding to 1 mol of silver) was added and reacted without stirring to reduce and precipitate silver particles.
Then, the silver particles were filtered, washed with water until the filtrate had a conductivity of 40 μS / cm or less, and dried to obtain silver powder (sample).
<比較例6>
銀濃度400g/Lの硝酸銀水溶液50mLを純水1Lに溶解させて硝酸銀水溶液を調製し、濃度25質量%のアンモニア水50mLを添加して攪拌することにより、銀アンミン錯体水溶液を得た。次いで、20℃の銀アンミン錯体水溶液に、溶存酸素濃度0.20〜2.00mg/Lに調整した、濃度11.9g/Lのヒドラジン水溶液1Lと濃度5g/Lのゼラチン水溶液48mL(銀1molに対して1.29gに相当)の混合溶液を加えて、撹拌することなく反応させて銀粒子を還元析出させた。
次いで、この銀粒子をろ過し、ろ液の伝導率が40μS/cm以下となるまで水洗後、乾燥させることにより銀粉(サンプル)を得た。
<Comparative Example 6>
A silver nitrate aqueous solution was obtained by dissolving 50 mL of a silver nitrate aqueous solution having a silver concentration of 400 g / L in 1 L of pure water to prepare a silver nitrate aqueous solution, adding 50 mL of ammonia water having a concentration of 25% by mass and stirring. Next, in a silver ammine complex aqueous solution at 20 ° C., 1 L of a hydrazine aqueous solution having a concentration of 11.9 g / L, adjusted to a dissolved oxygen concentration of 0.20 to 2.00 mg / L, and 48 mL of a gelatin aqueous solution having a concentration of 5 g / L (into 1 mol of silver). (Corresponding to 1.29 g), and the mixture was reacted without stirring to reduce and precipitate silver particles.
Then, the silver particles were filtered, washed with water until the filtrate had a conductivity of 40 μS / cm or less, and dried to obtain silver powder (sample).
(考察)
実施例の銀粉は、比較例の銀粉及び従来知られた銀粉に比べて大粒子でありながら、粒径が揃っているため、これを用いて銀ペーストを作製すれば、銀濃度を高くすることができ、均質で且つ、電気抵抗がより一層低い焼結導体を形成することができる。
このような観点から、本銀粉においては、SEMD50が2.50μm〜7.50μmであり、且つ、(SEMD90―SEMD10)/SEMD50≦0.50であるのが好ましいと考えることができる。
(Discussion)
Although the silver powder of the examples is larger than the silver powder of the comparative example and the conventionally known silver powder, the particle size is uniform, so if a silver paste is produced using this, the silver concentration is increased. It is possible to form a sintered conductor that is homogeneous and has a lower electrical resistance.
From this point of view, in this silver powder, SEM D50 is 2.50Myuemu~7.50Myuemu, and can be considered as preferably a (SEM D90- SEM D10) / SEM D50 ≦ 0.50 .
Claims (6)
走査型電子顕微鏡像(SEM)の画像解析により得られるD10(「SEMD10」と称する)、D50(「SEMD50」と称する)及びD90(「SEMD90」と称する)の関係が、関係式:(SEMD90―SEMD10)/SEMD50≦0.50で示されることを特徴とする銀粉。 D50 (referred to as “ SEM D50”) obtained by image analysis of a scanning electron microscope image (SEM) is 2.50 μm to 7.50 μm,
The relationship between D10 (referred to as “ SEM D10”), D50 (referred to as “ SEM D50”) and D90 (referred to as “ SEM D90”) obtained by image analysis of a scanning electron microscope image (SEM) is a relational expression: Silver powder characterized by being represented by ( SEM D90- SEM D10) / SEM D50 ≦ 0.50.
(TMA測定方法)(TMA measurement method)
銀粉を円柱状に成形し、この成形体の縦方向の線収縮率(%)を、熱機械分析装置(TMA)を用いて98mNの加重をかけながらAir雰囲気中20℃/分の昇温速度で測定し、500℃における熱収縮率(%)を求める。Silver powder is formed into a cylindrical shape, and the rate of linear shrinkage (%) in the vertical direction of this molded body is set to 20 ° C./min in an Air atmosphere while applying a weight of 98 mN using a thermomechanical analyzer (TMA). To determine the thermal shrinkage (%) at 500 ° C.
Sintered conductive paste made by using a silver powder according to any one of claims 1 to 5.
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PCT/JP2012/082330 WO2013136615A1 (en) | 2012-03-12 | 2012-12-13 | Silver powder |
KR1020147011996A KR20140089365A (en) | 2012-03-12 | 2012-12-13 | Silver powder |
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