JP2010077493A - Silver powder and method for producing the same - Google Patents
Silver powder and method for producing the same Download PDFInfo
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- JP2010077493A JP2010077493A JP2008247052A JP2008247052A JP2010077493A JP 2010077493 A JP2010077493 A JP 2010077493A JP 2008247052 A JP2008247052 A JP 2008247052A JP 2008247052 A JP2008247052 A JP 2008247052A JP 2010077493 A JP2010077493 A JP 2010077493A
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 107
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 18
- 229910052709 silver Inorganic materials 0.000 claims abstract description 36
- 239000004332 silver Substances 0.000 claims abstract description 36
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 35
- 150000002367 halogens Chemical class 0.000 claims abstract description 31
- 239000002245 particle Substances 0.000 claims abstract description 27
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 24
- 239000007864 aqueous solution Substances 0.000 claims abstract description 23
- -1 thereafter Substances 0.000 claims abstract description 23
- 239000003513 alkali Substances 0.000 claims abstract description 21
- 150000004820 halides Chemical class 0.000 claims abstract description 15
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000002270 dispersing agent Substances 0.000 claims abstract description 13
- 239000000243 solution Substances 0.000 claims abstract description 13
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 6
- 108010010803 Gelatin Proteins 0.000 claims abstract description 6
- 229920000159 gelatin Polymers 0.000 claims abstract description 6
- 239000008273 gelatin Substances 0.000 claims abstract description 6
- 235000019322 gelatine Nutrition 0.000 claims abstract description 6
- 235000011852 gelatine desserts Nutrition 0.000 claims abstract description 6
- 229910001961 silver nitrate Inorganic materials 0.000 claims abstract description 6
- 239000002518 antifoaming agent Substances 0.000 claims description 2
- 239000011347 resin Substances 0.000 abstract description 13
- 229920005989 resin Polymers 0.000 abstract description 13
- 238000010438 heat treatment Methods 0.000 abstract description 5
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 abstract description 4
- 239000013530 defoamer Substances 0.000 abstract 1
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 18
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 16
- 229910052801 chlorine Inorganic materials 0.000 description 16
- 239000000460 chlorine Substances 0.000 description 16
- 238000000034 method Methods 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 239000001103 potassium chloride Substances 0.000 description 9
- 235000011164 potassium chloride Nutrition 0.000 description 9
- 239000002002 slurry Substances 0.000 description 9
- 238000001914 filtration Methods 0.000 description 7
- 239000000853 adhesive Substances 0.000 description 6
- 230000001070 adhesive effect Effects 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000001723 curing Methods 0.000 description 5
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 239000004020 conductor Substances 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 229910000679 solder Inorganic materials 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- 102000008186 Collagen Human genes 0.000 description 2
- 108010035532 Collagen Proteins 0.000 description 2
- 229910021607 Silver chloride Inorganic materials 0.000 description 2
- 239000003985 ceramic capacitor Substances 0.000 description 2
- 229920001436 collagen Polymers 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 230000008602 contraction Effects 0.000 description 2
- 238000007872 degassing Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 238000013007 heat curing Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 108090000765 processed proteins & peptides Proteins 0.000 description 2
- 238000010079 rubber tapping Methods 0.000 description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 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
- 239000012190 activator Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000009826 distribution 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
- 238000000605 extraction Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 235000013373 food additive Nutrition 0.000 description 1
- 239000002778 food additive Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 238000004255 ion exchange chromatography Methods 0.000 description 1
- YWXYYJSYQOXTPL-SLPGGIOYSA-N isosorbide mononitrate Chemical compound [O-][N+](=O)O[C@@H]1CO[C@@H]2[C@@H](O)CO[C@@H]21 YWXYYJSYQOXTPL-SLPGGIOYSA-N 0.000 description 1
- 238000007561 laser diffraction method Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 102000004196 processed proteins & peptides Human genes 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229940096017 silver fluoride Drugs 0.000 description 1
- REYHXKZHIMGNSE-UHFFFAOYSA-M silver monofluoride Chemical compound [F-].[Ag+] REYHXKZHIMGNSE-UHFFFAOYSA-M 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000009283 thermal hydrolysis Methods 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
- Powder Metallurgy (AREA)
Abstract
Description
本発明は、銀粉およびその製造方法に関し、特に、電子部品の端子電極や回路基板パターンの形成に用いられる銀粉の製造方法に関する。 The present invention relates to silver powder and a method for producing the same, and more particularly to a method for producing silver powder used for forming terminal electrodes and circuit board patterns of electronic components.
従来、電子部品などの電極や回路を形成するために、銀粉を有機成分中に分散させた導電性ペーストが使用されている。一般に、導電性ペーストは、熱処理温度により焼成型ペーストと樹脂型ペーストに分類され、それぞれ用途や構成要素などが異なっている。 Conventionally, a conductive paste in which silver powder is dispersed in an organic component has been used to form electrodes and circuits such as electronic components. In general, the conductive paste is classified into a fired paste and a resin paste depending on the heat treatment temperature, and uses and components are different from each other.
焼成型ペーストは、構成要素として、銀粉、エチルセルロースやアクリル樹脂を有機溶剤に溶解したビヒクル、ガラスフリット、無機酸化物、有機溶剤、分散剤などを含み、ディッピング、印刷などにより所定パターンに形成された後、焼成されて導体を形成する。このような焼成型ペーストは、ハイブリッドＩＣ、積層セラミックコンデンサ、チップ抵抗器などの電極に使用されている。 The firing paste contains silver powder, a vehicle in which ethyl cellulose or acrylic resin is dissolved in an organic solvent, a glass frit, an inorganic oxide, an organic solvent, a dispersant, etc. as a constituent element, and is formed in a predetermined pattern by dipping, printing, or the like. Thereafter, it is fired to form a conductor. Such fired paste is used for electrodes of hybrid ICs, multilayer ceramic capacitors, chip resistors and the like.
一方、樹脂型ペーストは、構成要素として、銀粉、エポキシ樹脂やウレタン樹脂などの熱硬化性樹脂、硬化剤、有機溶剤、分散剤などを含み、ディスペンスや印刷などにより所定の導体パターンに形成された後に室温から１８０〜２５０℃程度の温度で硬化して、残存する樹脂の硬化収縮による銀粒子同士の接触により導電性が得ている。このような樹脂型ペーストは、スルーホールやメンブレンなどの配線材や導電性接着剤などに使用されている。なお、導電性接着剤は、鉛を含むはんだの代替として電子部品や回路基板の実装に用いられ、接合部の柔軟性や実装温度の低温化などのメリットが期待されている。 On the other hand, the resin-type paste contains silver powder, thermosetting resin such as epoxy resin and urethane resin, a curing agent, an organic solvent, a dispersing agent and the like as a constituent element, and is formed into a predetermined conductor pattern by dispensing or printing. Later, it is cured from room temperature to a temperature of about 180 to 250 ° C., and conductivity is obtained by contact between silver particles due to curing shrinkage of the remaining resin. Such a resin paste is used for wiring materials such as through holes and membranes, conductive adhesives, and the like. The conductive adhesive is used for mounting electronic components and circuit boards as a substitute for lead-containing solder, and is expected to have merits such as flexibility of the joint and lowering of the mounting temperature.
また、導電性ペーストにより形成された導体のはんだ濡れ性を改善するための活性剤としてハロゲン化物をフラックスに添加することが知られている（例えば、特許文献１参照）。また、はんだの代替として電子部品や回路基板の実装に使用する導電性接着剤の実装信頼性を向上させるために、導電性接着剤にハロゲンイオンを含む粒子を添加することが知られている（例えば、特許文献２参照）。 It is also known to add a halide to the flux as an activator for improving the solder wettability of a conductor formed from a conductive paste (see, for example, Patent Document 1). Moreover, in order to improve the mounting reliability of the conductive adhesive used for mounting electronic components and circuit boards as a substitute for solder, it is known to add particles containing halogen ions to the conductive adhesive ( For example, see Patent Document 2).
このようなハロゲン化物などを添加した導電性ペーストや導電性接着剤の原料として使用する銀粉に、予め塩化物のようなハロゲン化物などを添加することが試みられている。例えば、銀粉を塩酸水溶液のようなハロゲンイオンを含む水溶液に浸漬させた後、脱水し、乾燥させるか、あるいは、銀粉にハロゲン化銀を混合することによって、塩素などのハロゲンを有する銀粉を製造する方法が提案されている（例えば、特許文献３参照）。また、塩素ガス雰囲気中で塩素と銀粉末を反応させて銀粉末粒子の表面に塩化銀を形成させる方法も知られている（例えば、特許文献４参照）。 Attempts have been made to add halides such as chlorides in advance to silver powder used as a raw material for conductive pastes and conductive adhesives to which such halides are added. For example, silver powder having a halogen such as chlorine is produced by immersing the silver powder in an aqueous solution containing a halogen ion such as an aqueous hydrochloric acid solution, followed by dehydration and drying, or by mixing silver halide with the silver powder. A method has been proposed (see, for example, Patent Document 3). A method is also known in which chlorine and silver powder are reacted in a chlorine gas atmosphere to form silver chloride on the surface of silver powder particles (see, for example, Patent Document 4).
銀粉を樹脂型ペーストとして使用する場合、樹脂型ペーストはパターン形成された後、１８０℃〜２５０℃程度の温度で加熱硬化して、残存する樹脂の硬化収縮による銀粒子同士の接触により導電性を得ている。従来、前記加熱硬化の温度域における樹脂の収縮については、検討されていた。銀粉については、前記加熱硬化の温度域における収縮について、十分な検討がされていなかった。 When silver powder is used as a resin-type paste, the resin-type paste is heat-cured at a temperature of about 180 ° C. to 250 ° C. after the pattern is formed, and becomes conductive by contact between silver particles due to curing shrinkage of the remaining resin. It has gained. Conventionally, the shrinkage of the resin in the temperature range of the heat curing has been studied. About silver powder, sufficient examination was not carried out about the shrinkage | contraction in the temperature range of the said heat curing.
また、特許文献３に記載された方法のうち、銀粉を塩酸水溶液のようなハロゲンイオンを含む水溶液に浸漬させる方法では、銀粉を製造した後にハロゲンイオンを含む水溶液で処理することによって銀粉に塩素などのハロゲンを含有させているので、工程が多くなって手間がかかる。また、特許文献３に記載された方法のうち、銀粉にハロゲン化銀を混合する方法では、粒子径の相違などによって、銀粉とハロゲン化物を十分に均一に混合することが容易ではなく、局部的にハロゲン化銀が偏析し、品質が不安定になる。また、特許文献４の方法は、銀粉を製造した後に銀粉を塩素ガスで処理する工程が必要になるので、工数が多くなって手間がかかり、また、塩素ガスを５０〜１００ｐｐｍという高濃度で用いるので、塩素ガスの漏洩対策などが必要になり、設備コストやランニングコストがかかる。 Further, among the methods described in Patent Document 3, in a method in which silver powder is immersed in an aqueous solution containing halogen ions such as an aqueous hydrochloric acid solution, the silver powder is treated with an aqueous solution containing halogen ions and then silver or the like is added to the silver powder. Since the halogen is contained, the number of processes is increased and time is required. In addition, among the methods described in Patent Document 3, in the method of mixing silver halide with silver powder, it is not easy to mix silver powder and halide sufficiently uniformly due to the difference in particle diameter, etc. The silver halide segregates and the quality becomes unstable. Moreover, since the method of patent document 4 requires the process of processing silver powder with chlorine gas after manufacturing silver powder, man-hours increase and it takes time, and chlorine gas is used by high concentration of 50-100 ppm. Therefore, measures against leakage of chlorine gas are required, and equipment costs and running costs are required.
したがって、本発明は、このような従来の問題点に鑑み、樹脂型ペーストの硬化加熱温度における収縮率が高いハロゲンを含有する銀粉、および、前記ハロゲンを含有する銀粉を簡単且つ安価に製造することができる、銀粉の製造方法を提供することを目的とする。 Therefore, in view of such a conventional problem, the present invention is to easily and inexpensively produce a silver powder containing a halogen having a high shrinkage rate at a curing heating temperature of a resin paste, and a silver powder containing the halogen. An object of the present invention is to provide a method for producing silver powder.
本発明者らは、上記課題を解決するために鋭意研究した結果、２４０℃における銀粉の体積収縮率（以下、収縮率と記すことがある）は銀粉中のハロゲン含有量により変化することを見出し、銀粉中のハロゲン含有量を０．１質量％を超え、０．５質量％以下とすることにより、２４０℃における銀粉の収縮率が、０．７％以上のハロゲンを含有する銀粉を得ることができた。 As a result of intensive studies to solve the above problems, the present inventors have found that the volumetric shrinkage of silver powder at 240 ° C. (hereinafter sometimes referred to as shrinkage) varies depending on the halogen content in the silver powder. By obtaining a halogen content in silver powder exceeding 0.1% by mass and 0.5% by mass or less, the silver powder shrinkage rate at 240 ° C. is to obtain silver powder containing 0.7% or more of halogen. I was able to.
また、本発明者らは、上記課題を解決するために鋭意研究した結果、銀イオンを含有する水溶液に還元剤を添加した後、アルカリを添加し、このアルカリの添加中にハロゲン化物を添加して、ハロゲンを含有する銀粒子を生成させることにより、前記ハロゲンを含有する銀粉を簡単且つ安価に製造することができることを見出し、本発明を完成するに至った。 Further, as a result of intensive studies to solve the above problems, the present inventors have added a reducing agent to an aqueous solution containing silver ions, added an alkali, and added a halide during the addition of the alkali. Thus, it has been found that by producing silver particles containing halogen, the silver powder containing halogen can be produced easily and inexpensively, and the present invention has been completed.
すなわち、本発明による銀粉の製造方法は、銀イオンを含有する水溶液に還元剤を添加した後、アルカリを添加し、このアルカリの添加中にハロゲン化物を添加して、ハロゲンを含有する銀粒子を生成させることにより、ハロゲンを０．１質量％を超え、０．５質量％以下含有し、２４０℃における銀粉の収縮率が、０．７％以上である銀粉を得ることを特徴とする。この銀粉の製造方法において、銀イオンを含有する水溶液が硝酸銀水溶液であるのが好ましく、還元剤がホルマリンであるのが好ましい。また、アルカリが水酸化ナトリウムであるのが好ましく、ハロゲン化物が塩化物であるのが好ましい。また、アルカリを添加する前に、銀イオンを含有する水溶液に分散剤を添加するのが好ましく、分散剤がゼラチンであるのが好ましい。また、分散剤を添加する際に、銀イオンを含有する水溶液に消泡剤を添加するのが好ましい。 That is, in the method for producing silver powder according to the present invention, after adding a reducing agent to an aqueous solution containing silver ions, an alkali is added, a halide is added during the addition of the alkali, and silver particles containing halogen are obtained. By making it generate | occur | produce, it is characterized by obtaining the silver powder which contains a halogen exceeding 0.1 mass% and 0.5 mass% or less, and the shrinkage | contraction rate of the silver powder in 240 degreeC is 0.7% or more. In this silver powder production method, the aqueous solution containing silver ions is preferably an aqueous silver nitrate solution, and the reducing agent is preferably formalin. The alkali is preferably sodium hydroxide, and the halide is preferably chloride. Moreover, it is preferable to add a dispersing agent to the aqueous solution containing silver ions before adding the alkali, and the dispersing agent is preferably gelatin. Moreover, when adding a dispersing agent, it is preferable to add an antifoamer to the aqueous solution containing a silver ion.
本発明によれば、樹脂型ペーストの硬化加熱温度における収縮率が高いハロゲンを含有する銀粉を得ることができ、樹脂型ペースト硬化の際、樹脂の加熱収縮に加え、銀粉の収縮効果も大きくなることにより、硬化後の樹脂型ペーストの導電性を向上することが可能となる。また、銀イオンを含有する水溶液に還元剤を添加した後、アルカリを添加し、このアルカリの添加中にハロゲン化物を添加して、ハロゲンを含有する銀粒子を生成させることにより、前記ハロゲンを含有する銀粉を簡単且つ安価に製造することができる。 ADVANTAGE OF THE INVENTION According to this invention, the silver powder containing halogen with the high shrinkage rate in the curing heating temperature of resin type paste can be obtained, and in addition to heat shrinkage of resin at the time of resin type paste hardening, the shrinkage effect of silver powder also becomes large. As a result, the conductivity of the cured resin paste can be improved. Further, after adding a reducing agent to an aqueous solution containing silver ions, an alkali is added, and a halide is added during the addition of the alkali to produce silver particles containing halogen, thereby containing the halogen. The silver powder to be manufactured can be manufactured easily and inexpensively.
本発明による銀粉の製造方法の実施の形態では、銀イオンを含有する水溶液に還元剤を添加した後、アルカリを添加し、このアルカリの添加中にハロゲン化物を添加して、ハロゲンを含有する銀粒子を生成させて銀含有スラリーとし、その後、ろ過し、水洗し、乾燥させ、解砕して、ハロゲンを含有する銀粉を得る。本発明の銀粉の特徴であるハロゲン含有量を得るために必要な条件については後述する。 In the embodiment of the method for producing silver powder according to the present invention, after adding a reducing agent to an aqueous solution containing silver ions, an alkali is added, a halide is added during the addition of the alkali, and the silver containing halogen is added. Particles are produced to form a silver-containing slurry, which is then filtered, washed with water, dried and crushed to obtain a silver powder containing halogen. Conditions necessary for obtaining the halogen content, which is a feature of the silver powder of the present invention, will be described later.
コスト面から、銀イオンを含有する水溶液として硝酸銀水溶液を使用するのが好ましく、還元剤としてホルマリンを使用するのが好ましく、アルカリとして水酸化ナトリウムを使用するのが好ましい。なお、アルカリの添加は、連続的に行うのが好ましい。 In view of cost, it is preferable to use an aqueous silver nitrate solution as the aqueous solution containing silver ions, it is preferable to use formalin as the reducing agent, and it is preferable to use sodium hydroxide as the alkali. In addition, it is preferable to add the alkali continuously.
また、ハロゲン化物として塩化物を使用するのが好ましい。塩化銀の水への溶解度はフッ化銀などの他のハロゲン化銀より低いので、塩化物を使用すると、他のハロゲン化物を使用する場合よりもハロゲンを含有する銀粉を得るのが容易になる。また、銀粉中のハロゲン含有量は、２４０℃における銀粉の収縮率を高くするためには、乾燥銀粉量に対して０．１質量％を超えることが好ましい。０．１質量％以下の場合には、ハロゲンを添加する効果が十分でない。ハロゲン含有量が多過ぎるとハロゲンによる回路形成後の銀の腐食やマイグレーションなどの悪影響の発生を防止できない場合があり、ハロゲン含有量は、乾燥銀粉量に対して０．５質量％以下であるのが好ましい。製造される銀粉中のハロゲン含有量は、添加するハロゲン化物の量を変更することにより調整する。また、塩化物として塩化カリウムや塩化ナトリウムを使用するのが好ましい。塩化カリウムや塩化ナトリウムは、塩化アンモニウムなどのように水への溶解時に大きな吸収熱を生じることがなく、アンモニア臭の発生も無く、取り扱いが容易である。 It is also preferred to use chloride as the halide. Since the solubility of silver chloride in water is lower than other silver halides such as silver fluoride, the use of chloride makes it easier to obtain a silver powder containing halogen than when other halides are used. . Further, the halogen content in the silver powder is preferably more than 0.1% by mass with respect to the dry silver powder amount in order to increase the shrinkage rate of the silver powder at 240 ° C. In the case of 0.1% by mass or less, the effect of adding halogen is not sufficient. If there is too much halogen content, it may not be possible to prevent the occurrence of adverse effects such as corrosion and migration of silver after circuit formation by halogen, and the halogen content is 0.5% by mass or less with respect to the amount of dry silver powder. Is preferred. The halogen content in the silver powder to be produced is adjusted by changing the amount of halide to be added. Further, it is preferable to use potassium chloride or sodium chloride as the chloride. Potassium chloride and sodium chloride, such as ammonium chloride, do not generate large heat of absorption when dissolved in water, do not generate ammonia odor, and are easy to handle.
また、アルカリを添加する前に、銀イオンを含有する水溶液に分散剤を添加するのが好ましい。分散剤を添加すると、銀粉の分散性が良好になり、銀粉を含む接着剤やペーストを塗布した際に表面を均一にすることができる。この場合、分散剤として、ゼラチンやコラーゲンペプチドなどを使用するのが好ましい。ゼラチンやコラーゲンペプチドは、水溶性が高いので、反応時に溶解作業を行い易く、また、食品添加物としても用いられるので作業者にとって安全である。また、分散剤を添加する際に、銀イオンを含有する水溶液に消泡剤を添加するのが好ましい。なお、ろ過前の銀含有スラリーのｐＨは、８以下であるのが好ましく、収率を考慮すると６〜８であるのが好ましい。また、乾燥には真空乾燥器を使用するのが好ましい。 Moreover, before adding an alkali, it is preferable to add a dispersing agent to the aqueous solution containing silver ions. When a dispersant is added, the dispersibility of the silver powder is improved, and the surface can be made uniform when an adhesive or paste containing silver powder is applied. In this case, it is preferable to use gelatin or collagen peptide as a dispersant. Gelatin and collagen peptides are highly soluble in water, so that they can be easily dissolved during the reaction, and are also used as food additives, so that they are safe for workers. Moreover, when adding a dispersing agent, it is preferable to add an antifoamer to the aqueous solution containing a silver ion. In addition, it is preferable that the pH of the silver containing slurry before filtration is 8 or less, and it is preferable that it is 6-8 when a yield is considered. Moreover, it is preferable to use a vacuum dryer for drying.
銀粉の２４０℃における体積収縮率は、大きいほうが好ましく、具体的には、０．７％以上が好ましく、１．０％以上であることが更に好ましい。また、２％を超える場合、樹脂の収縮温度との関係等により、好ましくない場合がある。 The volume shrinkage rate at 240 ° C. of the silver powder is preferably large, specifically, 0.7% or more is preferable, and 1.0% or more is more preferable. Moreover, when it exceeds 2%, it may be unpreferable by the relationship with the shrinkage temperature of resin, etc.
以下、本発明による実施例について詳細に説明する。 Examples according to the present invention will be described in detail below.
［実施例１］
硝酸銀１ｋｇを５．３Lの純水に溶解して得られた硝酸銀水溶液に、３７％のホルムアルデヒド水溶液（ホルマリン）３８０ｇと、１００ｍＬの温水に溶解したゼラチン（ゼライス社製のＭ−６５５）５．７ｇとを加えるとともに、発泡を抑えるための消泡剤（第一工業製薬株式会社製のアンチフロスＦ−２４４）０．３ｇを加えて、２５℃に保持した。この溶液を攪拌しながら、この溶液に、２５℃に保持した純水３Ｌに水酸化ナトリウム４００gを溶解した水酸化ナトリウム水溶液を３０分間かけて連続添加して、銀粒子を生成させるとともに、この水酸化ナトリウム水溶液の連続添加の途中（水酸化ナトリウム水溶液の添加の開始から２５分後）に、２５℃に保持した水４０ｍＬに塩化カリウム１．８ｇを溶解した塩化カリウム溶液を一挙に加えた。この水酸化ナトリウム水溶液の添加が終了した後、得られた銀含有スラリーをろ過し、水洗（水洗液の電気伝導度が０．５ｍＳ／ｍ以下になるまで純水で洗浄）し、９０℃に設定した真空乾燥器で乾燥させ、解砕して銀粉を得た。なお、ろ過前の銀含有スラリーのｐＨは７．４であった。
[Example 1]
In a silver nitrate aqueous solution obtained by dissolving 1 kg of silver nitrate in 5.3 L of pure water, 380 g of 37% formaldehyde aqueous solution (formalin) and gelatin dissolved in 100 mL of warm water (M-655 manufactured by Zerais) 5.7 g And 0.3 g of an antifoaming agent (Anti-Floss F-244 manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) for suppressing foaming was added and kept at 25 ° C. While stirring this solution, an aqueous solution of sodium hydroxide in which 400 g of sodium hydroxide was dissolved in 3 L of pure water maintained at 25 ° C. was continuously added over 30 minutes to produce silver particles. During the continuous addition of the aqueous sodium oxide solution (25 minutes after the start of the addition of the aqueous sodium hydroxide solution), a potassium chloride solution in which 1.8 g of potassium chloride was dissolved in 40 mL of water maintained at 25 ° C. was added all at once. After the addition of the aqueous sodium hydroxide solution is completed, the obtained silver-containing slurry is filtered, washed with water (washed with pure water until the electrical conductivity of the washing solution is 0.5 mS / m or less), and the temperature is 90 ° C. It dried with the set vacuum dryer and crushed and obtained silver powder. In addition, pH of the silver containing slurry before filtration was 7.4.
このようにして得られた銀粉について、収縮率、ＢＥＴ比表面積、タップ密度、平均粒径Ｄ５０（マイクロトラック）および塩素含有量を測定した。 The silver powder thus obtained was measured for shrinkage rate, BET specific surface area, tap density, average particle diameter D 50 (Microtrac) and chlorine content.
銀粉の収縮率は、直径５ｍｍの金型に入れた銀粉０．１５ｇに５０ｋｇｆの加重をかけて作製したペレット状の銀粉試料を、膨張率測定装置（マック・サイエンス／ブルカー・エイエックスエス株式会社製のＤＩＬＡＴＯ ＭＥＴＡＥＲ ５０１０型）を用いて、３０℃から６００℃まで昇温速度１０℃／分で加熱した場合の試料の長さを測定し、次式により求めた。
２４０℃における収縮率（％）＝（Ｌ３０−Ｌ２４０）／Ｌ３０×１００
ここで、Ｌ３０、Ｌ２４０はそれぞれ、試料温度が３０℃、２４０℃におけるペレット状の銀粉試料の長さ（ｍｍ）である。
The shrinkage rate of silver powder was determined by using a pellet-shaped silver powder sample prepared by applying 50 kgf of weight to 0.15 g of silver powder placed in a 5 mm diameter mold, and an expansion coefficient measuring device (Mac Science / Bruker AXS Co., Ltd.). The length of the sample when heated from 30 ° C. to 600 ° C. at a heating rate of 10 ° C./min was measured using a DILATO METAER 5010 model), and was obtained by the following formula.
Shrinkage rate at 240 ° C. (%) = (L 30 −L 240 ) / L 30 × 100
Here, L 30 and L 240 are the length (mm) of the pellet-shaped silver powder sample at the sample temperatures of 30 ° C. and 240 ° C., respectively.
ＢＥＴ比表面積は、カウンタクローム社製のモノソーブによって、脱気温度６０℃、脱気時間１０分間で測定した。 The BET specific surface area was measured with a monosorb manufactured by Counterchrome at a degassing temperature of 60 ° C. and a degassing time of 10 minutes.
タップ密度は、タップ比重測定器（柴山科学製のカサ比重測定器ＳＳ−ＤＡ−２型）を使用し、銀粉試料１５ｇを計量して、容器（２０ｍＬ試験管）に入れ、落差２０ｍｍで１０００回タッピングし、タップ密度＝試料重量（１５ｇ）／タッピング後の試料体積（ｃｍ３）から算出した。 The tap density was measured using a tap specific gravity measuring device (Casa specific gravity measuring device SS-DA-2 manufactured by Shibayama Kagaku), weighing 15 g of a silver powder sample, and placing it in a container (20 mL test tube), 1000 times with a drop of 20 mm. Tapping and calculating from tap density = sample weight (15 g) / sample volume (cm 3 ) after tapping.
平均粒径Ｄ５０は、銀粉試料０．３ｇをイソプロピルアルコール５０ｍＬに入れ、出力５０Ｗ超音波洗浄器で５分間分散させた後、マイクロトラック粒度分布測定装置（ハネウエル−日機装製の９３２０−Ｘ１００）によってレーザー回折法で測定した際のＤ５０（累積５０質量％粒径）の値である。 The average particle diameter D 50 is put silver powder sample 0.3g of isopropyl alcohol 50 mL, was dispersed for 5 minutes at an output 50W ultrasonic cleaner, Microtrac particle size distribution measuring apparatus - by (Honeywell manufactured by Nikkiso Co. of 9320-X100) It is the value of D 50 (cumulative 50% by mass particle size) when measured by a laser diffraction method.
得られた銀粉中の塩素含有量は、銀粉１．０ｇを燃焼ボートに載せて、予め１０００℃に加熱した電気管状炉に装入し、キャリアガス（Ｏ２）によって水蒸気を送って、吸収瓶中のアルカリ水溶液に水蒸気を捕集・吸収させる熱加水分解法による分解抽出を行い、吸収液をイオンクロマトグラフィーで測定することにより求めた。 The obtained silver powder has a chlorine content of 1.0 g of silver powder placed on a combustion boat, charged in an electric tubular furnace preheated to 1000 ° C., sent with water vapor using a carrier gas (O 2 ), and an absorption bottle. It was obtained by performing decomposition extraction by a thermal hydrolysis method in which water vapor was collected and absorbed in the aqueous alkali solution, and the absorption liquid was measured by ion chromatography.
その結果、２４０℃における収縮率は０．８３％、ＢＥＴ比表面積は２．６ｍ２／ｇ、タップ密度は２．１ｇ／ｃｍ３、平均粒径Ｄ５０は４．４μm、塩素含有量は０．１１質量％であった。 As a result, the shrinkage at 240 ° C. was 0.83%, the BET specific surface area was 2.6 m 2 / g, the tap density was 2.1 g / cm 3 , the average particle size D 50 was 4.4 μm, and the chlorine content was 0. It was 11 mass%.
［実施例２］
添加する塩化カリウムの量を３．６ｇとした以外は、実施例１と同様の方法で、銀粉を製造した。なお、ろ過前の銀含有スラリーのｐＨは７．６であった。
[Example 2]
Silver powder was produced in the same manner as in Example 1 except that the amount of potassium chloride to be added was 3.6 g. The pH of the silver-containing slurry before filtration was 7.6.
このようにして得られた銀粉について、実施例１と同様の方法により、収縮率、ＢＥＴ比表面積、タップ密度、平均粒径Ｄ５０（マイクロトラック）および塩素の含有量を測定した。その結果、２４０℃における収縮率は１．２４％、ＢＥＴ比表面積は２．７ｍ２／ｇ、タップ密度は１．９ｇ／ｃｍ３、平均粒径Ｄ５０は３．５μm、塩素含有量は０．２２質量％であった。 With respect to the silver powder thus obtained, the shrinkage rate, BET specific surface area, tap density, average particle diameter D 50 (Microtrac) and chlorine content were measured by the same method as in Example 1. As a result, the shrinkage rate at 240 ° C. was 1.24%, the BET specific surface area was 2.7 m 2 / g, the tap density was 1.9 g / cm 3 , the average particle size D50 was 3.5 μm, and the chlorine content was 0.8. It was 22 mass%.
［実施例３］
添加する塩化カリウムの量を７．２ｇとした以外は、実施例１と同様の方法で、銀粉を製造した。なお、ろ過前の銀含有スラリーのｐＨは７．９であった。
[Example 3]
Silver powder was produced in the same manner as in Example 1 except that the amount of potassium chloride to be added was 7.2 g. In addition, pH of the silver containing slurry before filtration was 7.9.
このようにして得られた銀粉について、実施例１と同様の方法により、収縮率、ＢＥＴ比表面積、タップ密度、平均粒径Ｄ５０（マイクロトラック）および塩素含有量を測定した。
その結果、２４０℃における収縮率は１．３１％、ＢＥＴ比表面積は２．７ｍ２／ｇ、タップ密度は１．９ｇ／ｃｍ３、平均粒径は４．０μm、塩素含有量は０．３９質量％であった。
With respect to the silver powder thus obtained, the shrinkage rate, BET specific surface area, tap density, average particle diameter D 50 (Microtrac) and chlorine content were measured by the same method as in Example 1.
As a result, the shrinkage rate at 240 ° C. was 1.31%, the BET specific surface area was 2.7 m 2 / g, the tap density was 1.9 g / cm 3 , the average particle size was 4.0 μm, and the chlorine content was 0.39. It was mass%.
［比較例１］
添加する塩化カリウムの量を０．９ｇとした以外は、実施例１と同様の方法で、銀粉を製造した。なお、ろ過前の銀含有スラリーのｐＨは６．６であった。
[Comparative Example 1]
Silver powder was produced in the same manner as in Example 1 except that the amount of potassium chloride to be added was 0.9 g. The pH of the silver-containing slurry before filtration was 6.6.
このようにして得られた銀粉について、実施例１と同様の方法により、収縮率、ＢＥＴ比表面積、タップ密度、平均粒径Ｄ５０（マイクロトラック）および塩素含有量を測定した。その結果、２４０℃における収縮率は０．４５％、ＢＥＴ比表面積は２．７ｍ２／ｇ、タップ密度は２．３ｇ／ｃｍ３、平均粒径は３．７μm、塩素含有量は０．０６質量％であった。この比較例では、２４０℃における収縮率が実施例と比較して小さかった。 With respect to the silver powder thus obtained, the shrinkage rate, BET specific surface area, tap density, average particle diameter D 50 (Microtrac), and chlorine content were measured by the same method as in Example 1. As a result, the shrinkage at 240 ° C. was 0.45%, the BET specific surface area was 2.7 m 2 / g, the tap density was 2.3 g / cm 3 , the average particle size was 3.7 μm, and the chlorine content was 0.06. It was mass%. In this comparative example, the shrinkage rate at 240 ° C. was smaller than that of the example.
［比較例２］
塩化カリウムを添加しなかった以外は、実施例１と同様の方法で、銀粉を製造した。なお、ろ過前の銀含有スラリーのｐＨは６．６であった。
[Comparative Example 2]
Silver powder was produced in the same manner as in Example 1 except that potassium chloride was not added. The pH of the silver-containing slurry before filtration was 6.6.
このようにして得られた銀粉について、実施例１と同様の方法により、収縮率、ＢＥＴ比表面積、タップ密度、平均粒径Ｄ５０（マイクロトラック）および塩素含有量を測定した。その結果、２４０℃における収縮率は０．１３％、ＢＥＴ比表面積は２．６ｍ２／ｇ、タップ密度は２．４ｇ／ｃｍ３、平均粒径は３．２μm、塩素含有量は０．００１質量％未満であった。この比較例では、塩素含有量が検出限界以下であり、２４０℃における収縮率が実施例と比較して非常に小さい値となった。 With respect to the silver powder thus obtained, the shrinkage rate, BET specific surface area, tap density, average particle diameter D 50 (Microtrac), and chlorine content were measured by the same method as in Example 1. As a result, the shrinkage rate at 240 ° C. was 0.13%, the BET specific surface area was 2.6 m 2 / g, the tap density was 2.4 g / cm 3 , the average particle size was 3.2 μm, and the chlorine content was 0.001. It was less than mass%. In this comparative example, the chlorine content was below the detection limit, and the shrinkage rate at 240 ° C. was a very small value compared to the example.
［比較例３］
添加する塩化カリウムの量を１．１ｇとした以外は、実施例１と同様の方法で、銀粉を製造した。なお、ろ過前の銀含有スラリーのｐＨは６．６であった。
[Comparative Example 3]
Silver powder was produced in the same manner as in Example 1 except that the amount of potassium chloride to be added was 1.1 g. The pH of the silver-containing slurry before filtration was 6.6.
このようにして得られた銀粉について、実施例１と同様の方法により、収縮率、ＢＥＴ比表面積、タップ密度、平均粒径Ｄ５０（マイクロトラック）および塩素含有量を測定した。その結果、２４０℃における収縮率は０．６０％、ＢＥＴ比表面積は２．７ｍ２／ｇ、タップ密度は２．３ｇ／ｃｍ３、平均粒径は４．２μm、塩素含有量は０．０８質量％であった。この比較例では、２４０℃における収縮率が実施例と比較して小さかった。 With respect to the silver powder thus obtained, the shrinkage rate, BET specific surface area, tap density, average particle diameter D 50 (Microtrac) and chlorine content were measured by the same method as in Example 1. As a result, the shrinkage rate at 240 ° C. was 0.60%, the BET specific surface area was 2.7 m 2 / g, the tap density was 2.3 g / cm 3 , the average particle size was 4.2 μm, and the chlorine content was 0.08. It was mass%. In this comparative example, the shrinkage rate at 240 ° C. was smaller than that of the example.
本発明の銀粉の製造方法によって製造された銀粉は、積層セラミックコンデンサの内部電極、回路基板の導体パターン、太陽電池やプラズマディスプレイパネル用基板の電極、回路などの電子部品などに利用することができ、特に樹脂型ペースト用の銀粉として好適に利用できる。 The silver powder produced by the silver powder production method of the present invention can be used for internal electrodes of multilayer ceramic capacitors, conductor patterns of circuit boards, electrodes of substrates for solar cells and plasma display panels, electronic components such as circuits, and the like. In particular, it can be suitably used as a silver powder for resin-type paste.
Claims (9)
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| JP2008247052A JP2010077493A (en) | 2008-09-26 | 2008-09-26 | Silver powder and method for producing the same |
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| JP2008247052A JP2010077493A (en) | 2008-09-26 | 2008-09-26 | Silver powder and method for producing the same |
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| JP2010077493A true JP2010077493A (en) | 2010-04-08 |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012041570A (en) * | 2010-08-12 | 2012-03-01 | Dowa Holdings Co Ltd | Silver powder, method of manufacturing the same, conductive paste and electronic component |
| JP2012197487A (en) * | 2011-03-22 | 2012-10-18 | Mitsubishi Paper Mills Ltd | Method for producing metal ultrafine particle and composition containing the metal ultrafine particle |
| CN103406550A (en) * | 2013-08-26 | 2013-11-27 | 中科铜都粉体新材料股份有限公司 | Method for preparing silver micro-powder for electronic paste of pressure sensitive element |
| KR20180121190A (en) * | 2017-04-28 | 2018-11-07 | 대주전자재료 주식회사 | Silver particle containing inner void and method of manufacture thereof |
| CN116571734A (en) * | 2023-07-13 | 2023-08-11 | 深圳市哈深智材科技有限公司 | Silver particles and preparation method and application thereof |
-
2008
- 2008-09-26 JP JP2008247052A patent/JP2010077493A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012041570A (en) * | 2010-08-12 | 2012-03-01 | Dowa Holdings Co Ltd | Silver powder, method of manufacturing the same, conductive paste and electronic component |
| JP2012197487A (en) * | 2011-03-22 | 2012-10-18 | Mitsubishi Paper Mills Ltd | Method for producing metal ultrafine particle and composition containing the metal ultrafine particle |
| CN103406550A (en) * | 2013-08-26 | 2013-11-27 | 中科铜都粉体新材料股份有限公司 | Method for preparing silver micro-powder for electronic paste of pressure sensitive element |
| KR20180121190A (en) * | 2017-04-28 | 2018-11-07 | 대주전자재료 주식회사 | Silver particle containing inner void and method of manufacture thereof |
| KR102033542B1 (en) | 2017-04-28 | 2019-10-17 | 대주전자재료 주식회사 | Silver particle containing inner void and method of manufacture thereof |
| CN116571734A (en) * | 2023-07-13 | 2023-08-11 | 深圳市哈深智材科技有限公司 | Silver particles and preparation method and application thereof |
| CN116571734B (en) * | 2023-07-13 | 2023-09-26 | 深圳市哈深智材科技有限公司 | Silver particles and preparation method and application thereof |
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