JPWO2019150732A1 - Silver oxalate - Google Patents
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- JPWO2019150732A1 JPWO2019150732A1 JP2019527265A JP2019527265A JPWO2019150732A1 JP WO2019150732 A1 JPWO2019150732 A1 JP WO2019150732A1 JP 2019527265 A JP2019527265 A JP 2019527265A JP 2019527265 A JP2019527265 A JP 2019527265A JP WO2019150732 A1 JPWO2019150732 A1 JP WO2019150732A1
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- XNGYKPINNDWGGF-UHFFFAOYSA-L silver oxalate Chemical compound [Ag+].[Ag+].[O-]C(=O)C([O-])=O XNGYKPINNDWGGF-UHFFFAOYSA-L 0.000 title claims abstract description 84
- 238000004455 differential thermal analysis Methods 0.000 claims abstract description 27
- 230000004580 weight loss Effects 0.000 claims abstract description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 39
- 238000002411 thermogravimetry Methods 0.000 claims description 28
- 238000000634 powder X-ray diffraction Methods 0.000 claims description 17
- 235000006408 oxalic acid Nutrition 0.000 claims description 13
- 229910052709 silver Inorganic materials 0.000 claims description 9
- 239000004332 silver Substances 0.000 claims description 9
- 238000010586 diagram Methods 0.000 abstract 1
- 238000005259 measurement Methods 0.000 abstract 1
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 38
- 239000007864 aqueous solution Substances 0.000 description 26
- 239000013078 crystal Substances 0.000 description 19
- 229910001961 silver nitrate Inorganic materials 0.000 description 19
- 238000002441 X-ray diffraction Methods 0.000 description 15
- 239000007788 liquid Substances 0.000 description 14
- 238000004458 analytical method Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 11
- GEVPUGOOGXGPIO-UHFFFAOYSA-N oxalic acid;dihydrate Chemical compound O.O.OC(=O)C(O)=O GEVPUGOOGXGPIO-UHFFFAOYSA-N 0.000 description 11
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 9
- 239000000243 solution Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 4
- 230000007423 decrease Effects 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000000976 ink Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000010944 silver (metal) Substances 0.000 description 2
- 229940100890 silver compound Drugs 0.000 description 2
- 150000003379 silver compounds Chemical class 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- HDCUKDHYRMGLRT-UHFFFAOYSA-L [Ag+2].[O-]C(=O)C([O-])=O Chemical class [Ag+2].[O-]C(=O)C([O-])=O HDCUKDHYRMGLRT-UHFFFAOYSA-L 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 150000004683 dihydrates Chemical class 0.000 description 1
- IRXRGVFLQOSHOH-UHFFFAOYSA-L dipotassium;oxalate Chemical compound [K+].[K+].[O-]C(=O)C([O-])=O IRXRGVFLQOSHOH-UHFFFAOYSA-L 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000010946 fine silver Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- -1 oxalate ions Chemical class 0.000 description 1
- PFPYHYZFFJJQFD-UHFFFAOYSA-N oxalic anhydride Chemical compound O=C1OC1=O PFPYHYZFFJJQFD-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C55/00—Saturated compounds having more than one carboxyl group bound to acyclic carbon atoms
- C07C55/02—Dicarboxylic acids
- C07C55/06—Oxalic acid
- C07C55/07—Salts thereof
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/41—Preparation of salts of carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic System
- C07F1/10—Silver compounds
Abstract
熱重量測定において、１％重量減温度が１９０℃以上であることを特徴とするシュウ酸銀。また、示差熱分析において、最大温度が２１９℃以上であることを特徴とするシュウ酸銀。本発明は、熱安定性に優れたシュウ酸銀を提供することを課題とし、熱安定性を向上させることで、爆発性を低下させ、工業的に利用され易いシュウ酸銀を提供することができる。【選択図】なしSilver oxalate having a 1% weight loss temperature of 190 ° C. or higher in thermogravimetric measurement. Silver oxalate characterized by having a maximum temperature of 219 ° C. or higher in a differential thermal analysis. An object of the present invention is to provide silver oxalate having excellent thermal stability, and by improving thermal stability, reducing explosiveness and providing silver oxalate which is easily used industrially. it can. [Selection diagram] None
Description
本発明は、シュウ酸銀に関する。 The present invention relates to silver oxalate.
銀（Ａｇ）は、特に優れた導電性を有することから、導電性ペーストや導電性インクなどの用途に利用されている。これらの用途に利用する場合には、その用途に適した銀の形態に加工されることとなるが、各種形態の銀を生成する際には、要求される性状に応じた銀化合物が中間体として利用される。 Since silver (Ag) has particularly excellent conductivity, it is used for applications such as conductive pastes and conductive inks. When used in these applications, it will be processed into a silver form suitable for the application, but when producing various forms of silver, a silver compound according to the required properties is an intermediate Used as
たとえば、銀化合物であるシュウ酸銀（Ａｇ２Ｃ２Ｏ４）は、銀粒子などを製造する際の前駆体として利用されることが報告されている。シュウ酸銀は、還元剤を要することなく比較的低温で熱分解し、微細な銀粒子を生成することができるという特長を有し、また、このとき放出されるシュウ酸イオン（Ｃ２Ｏ４ ２−）は、二酸化炭素として除去されるため、不純物が残留しないという利点がある。For example, it has been reported that silver oxalate (Ag 2 C 2 O 4 ) which is a silver compound is used as a precursor when producing silver particles and the like. Silver oxalate has a feature that it can be thermally decomposed at a relatively low temperature without requiring a reducing agent to produce fine silver particles, and oxalate ions (C 2 O 4 Since 2- ) is removed as carbon dioxide, there is an advantage that impurities do not remain.
シュウ酸銀に関して、特許文献１には、硝酸銀溶液とシュウ酸カリウムとを混合してシュウ酸銀を製造すること、また、含水率の低く付着性のない取扱い容易なシュウ酸銀を沈殿することが記載されている。また、特許文献２には、シュウ酸銀を、水系や有機系の溶液にシュウ酸銀を懸濁させることで、爆発性を低減させ取扱い性を改善することが記載されている。 Regarding silver oxalate, Patent Literature 1 discloses that silver oxalate is produced by mixing a silver nitrate solution and potassium oxalate, and that silver oxalate having a low water content and having no stickiness and easy to handle is precipitated. Is described. Patent Literature 2 describes that silver oxalate is suspended in an aqueous or organic solution to reduce explosive properties and improve handleability.
本発明の実施形態は、熱安定性に優れたシュウ酸銀を提供することを目的とする。 An embodiment of the present invention aims to provide silver oxalate having excellent thermal stability.
１）本発明の実施形態に係るシュウ酸銀は、熱重量測定において、１％重量減温度が１９０℃以上であることを特徴とする。
２）本発明の実施形態に係るシュウ酸銀は、示差熱分析において、最大温度が２１９℃以上であることを特徴とする。
３）本発明の実施形態に係るシュウ酸銀は、ＣｕＫα線を用いた粉末Ｘ線回折パターンにおいて、２θが１７．２°±３°または２８．８°±３°で最大のピーク強度を示すことを特徴とする上記１）又は２）に記載のシュウ酸銀である。
４）本発明の実施形態に係るシュウ酸銀は、ＣｕＫα線を用いた粉末Ｘ線回折パターンにおいて、２θが１７．２°±３°、２８．８°±３°、２９．８°±３°、３２．３°±３°、４４．９°±３°および、５３．２°±３°のいずれかに、主要なピークを示すことを特徴とする上記１）又は２）に記載のシュウ酸銀である。1) The silver oxalate according to the embodiment of the present invention has a 1% weight loss temperature of 190 ° C. or more in thermogravimetry.
2) The silver oxalate according to the embodiment of the present invention is characterized by having a maximum temperature of 219 ° C. or higher in differential thermal analysis.
Silver oxalate according to Embodiment 3) The present invention, in the powder X-ray diffraction pattern using Cu K alpha line, 2 [Theta] is the maximum peak intensity at 17.2 ° ± 3 ° or 28.8 ° ± 3 ° The silver oxalate as described in 1) or 2) above,
4) The silver oxalate according to the embodiment of the present invention has a 2θ of 17.2 ° ± 3 °, 28.8 ° ± 3 °, 29.8 ° ± 3 in the powder X-ray diffraction pattern using CuKα ray. (1) or (2), (32.3 ° ± 3 °, 44.9 ° ± 3 °, and 53.2 ° ± 3 °). It is silver oxalate.
本発明の実施形態によれば、熱安定性に優れたシュウ酸銀を製造することができる。 According to the embodiment of the present invention, silver oxalate having excellent thermal stability can be produced.
シュウ酸銀は、１４０℃以上で発熱分解を開始し、２００℃以上で爆発的に分解するため、その取扱いに注意が必要な材料である。特に、急激な加熱、摩擦、衝撃によって爆発的に分解し、また、その威力も極めて高いことから、製造、保管、使用等において、細心の注意が必要である。このようなことから、シュウ酸銀の熱安定性を向上させて、爆発性を低下させることで、工業的に利用され易いシュウ酸銀が求められる。 Silver oxalate starts exothermic decomposition at 140 ° C. or higher, and explosively decomposes at 200 ° C. or higher. In particular, it decomposes explosively due to rapid heating, friction, and impact, and its power is extremely high. Therefore, careful attention must be paid to production, storage, use, and the like. For these reasons, there is a need for silver oxalate that can be easily used industrially by improving the thermal stability of silver oxalate and reducing the explosiveness.
シュウ酸銀の熱安定性について鋭意研究したところ、シュウ酸銀の合成条件を厳密に制御することによって、熱安定性に優れたシュウ酸銀を製造することができるとの知見が得られた。また、そのような熱安定性に優れたシュウ酸銀は特有の結晶構造を有するとの知見が得られた。本開示は、これらの知見に基づいて、以下の実施形態を提供するものである。 As a result of intensive studies on the thermal stability of silver oxalate, it was found that by strictly controlling the synthesis conditions of silver oxalate, it is possible to produce silver oxalate having excellent thermal stability. Further, it has been found that such silver oxalate having excellent thermal stability has a unique crystal structure. The present disclosure provides the following embodiments based on these findings.
本発明の実施形態に係るシュウ酸銀は、優れた熱安定を有し、熱重量測定（ＴＧ）における１％重量減温度が１９０℃以上と高い値を示すことを特徴とする。市販されているシュウ酸銀の中には１４０℃で分解するもの、すなわち、１％重量減温度が１４０℃のものもあることから、本発明の実施形態に係るシュウ酸銀が、熱安定性において格段に優れていることが理解できる。より好ましくは、熱重量測定（ＴＧ）における１％重量減温度が２００℃以上である。 The silver oxalate according to the embodiment of the present invention has excellent thermal stability, and a 1% weight loss temperature in thermogravimetry (TG) as high as 190 ° C. or more. Since some commercially available silver oxalates decompose at 140 ° C., that is, those having a 1% weight loss temperature of 140 ° C., the silver oxalate according to the embodiment of the present invention has thermal stability. It can be understood that the above is remarkably excellent. More preferably, the 1% weight loss temperature in thermogravimetry (TG) is 200 ° C. or more.
また、本発明の実施形態に係るシュウ酸銀は、示差熱分析（ＤＴＡ）における最大温度が２１９℃以上と高い値を示すものである。このように熱への安定性が向上したことにより、工業的に様々な用途において、シュウ酸銀を安全に利用することが可能となるという優れた効果を有する。 Further, the silver oxalate according to the embodiment of the present invention has a high maximum temperature of 219 ° C. or more in differential thermal analysis (DTA). The improved heat stability has an excellent effect that silver oxalate can be used safely in various industrial applications.
また、上述の熱安定性に優れたシュウ酸銀は、特有の結晶構造を有するものであり、具体的には、ＣｕＫα線を用いた粉末Ｘ線回折（ＸＲＤ）パターンにおいて、２θが１７．２°±３°または、２８．８°±３°で最大ピーク強度を示すことを特徴とする。なお、本開示において、±３°とは、ＸＲＤのピーク位置のずれ（シフト）を考慮したものである。Further, silver oxalate having excellent thermal stability described above is one having a unique crystal structure, specifically, in the powder X-ray diffraction (XRD) patterns using Cu K alpha line, 2 [Theta] 17. It is characterized by showing a maximum peak intensity at 2 ° ± 3 ° or 28.8 ° ± 3 °. In the present disclosure, ± 3 ° is based on a shift (shift) of the XRD peak position.
また、上述の熱安定性に優れたシュウ酸銀は、ＣｕＫα線を用いた粉末Ｘ線回折（ＸＲＤ）パターンにおいて、２θが１７．２°±３°、２８．８°±３°、２９．８°±３°、３２．３°±３°、４４．９°±３°、および、５３．２°±３°、に主要なピークを示すことを特徴とする。ここで「主要なピーク」とは、ピーク強度が大きいものから順に５番目までのピークを意味するものとする。Further, silver oxalate having excellent thermal stability described above, in the powder X-ray diffraction (XRD) patterns using Cu K alpha line, 2 [Theta] is 17.2 ° ± 3 °, 28.8 ° ± 3 °, 29 It is characterized by showing major peaks at 0.8 ° ± 3 °, 32.3 ° ± 3 °, 44.9 ° ± 3 °, and 53.2 ° ± 3 °. Here, the “main peak” means the fifth to fifth peaks in descending order of peak intensity.
次に、本発明の実施形態に係るシュウ酸銀の製造方法について説明する。
まず、硝酸銀を水に溶解して硝酸銀水溶液を調整し、また、シュウ酸・二水和物を水に溶解してシュウ酸水溶液を調整する。このとき、硝酸銀水溶液中の銀濃度は、０．７５ｍｏｌ／Ｌ以上３ｍｏｌ／Ｌ以下とし、シュウ酸水溶液中のシュウ酸濃度は、０．５ｍｏｌ／Ｌ以上１ｍｏｌ／Ｌ以下とする。これらの濃度が低すぎると熱安定性に優れたシュウ酸銀が析出し難く、一方、これらの濃度が高すぎると、反応中に硝酸銀又はシュウ酸が析出して、シュウ酸銀中に混入し、シュウ酸銀の熱安定性を低下させることがある。好ましくは、硝酸銀水溶液中の銀濃度は２ｍｏｌ／Ｌ以上３ｍｏｌ／Ｌ以下、シュウ酸水溶液中のシュウ酸濃度は０．５ｍｏｌ／Ｌ以上０．８ｍｏｌ／Ｌ以下とする。Next, a method for producing silver oxalate according to an embodiment of the present invention will be described.
First, a silver nitrate aqueous solution is prepared by dissolving silver nitrate in water, and an oxalic acid aqueous solution is prepared by dissolving oxalic acid / dihydrate in water. At this time, the silver concentration in the aqueous silver nitrate solution is 0.75 mol / L or more and 3 mol / L or less, and the oxalic acid concentration in the oxalic acid aqueous solution is 0.5 mol / L or more and 1 mol / L or less. If these concentrations are too low, silver oxalate with excellent thermal stability is difficult to precipitate, while if these concentrations are too high, silver nitrate or oxalic acid precipitates during the reaction and is mixed into silver oxalate. In some cases, the thermal stability of silver oxalate may be reduced. Preferably, the silver concentration in the aqueous silver nitrate solution is 2 mol / L or more and 3 mol / L or less, and the oxalic acid concentration in the oxalic acid aqueous solution is 0.5 mol / L or more and 0.8 mol / L or less.
次に硝酸銀水溶液に、定量ポンプを使用してシュウ酸水溶液を添加し、撹拌しながら混合、合成する。シュウ酸水溶液を滴下したのは、シュウ酸銀に製造設備から銀が混入することを防止するためであり、銀が混入すると、銀が酸化触媒の働きをして、シュウ酸銀の熱安定性に悪影響を与えることがある。また、金属不純物の混入を防ぐために、上記シュウ酸水和物の他、また、シュウ酸無水和物を用いることが好ましい。 Next, an aqueous oxalic acid solution is added to the aqueous silver nitrate solution using a metering pump, and mixed and synthesized with stirring. The aqueous oxalic acid solution was dropped to prevent silver from being mixed into the silver oxalate from the manufacturing equipment. When silver was mixed, the silver acted as an oxidation catalyst and the thermal stability of silver oxalate was reduced. May be adversely affected. In order to prevent metal impurities from being mixed, it is preferable to use oxalic anhydride in addition to the above oxalic hydrate.
熱安定性に優れたシュウ酸銀を作製するためには、合成時の液温および撹拌保持時間が特に重要である。液温が２０℃未満であると硝酸銀やシュウ酸の溶解度が低下し、一方、４０℃を超えると合成したシュウ酸銀の熱安定性が低下することから、液温は、２０〜４０℃とすることが好ましい。また、撹拌保持時間は３０分以上とするのが好ましく、また、液温によるが、懸濁条件下で長時間反応させると、シュウ酸銀の熱安定性が低下する傾向にあることから、液温が高い場合は、撹拌保持時間は４時間以内とすることが好ましい。 In order to produce silver oxalate having excellent thermal stability, the liquid temperature and the stirring and holding time during synthesis are particularly important. If the liquid temperature is less than 20 ° C, the solubility of silver nitrate or oxalic acid decreases, while if it exceeds 40 ° C, the thermal stability of the synthesized silver oxalate decreases. Is preferred. Further, the stirring and holding time is preferably 30 minutes or more, and although it depends on the liquid temperature, if the reaction is carried out for a long time under suspension conditions, the thermal stability of silver oxalate tends to decrease. When the temperature is high, the stirring and holding time is preferably within 4 hours.
その後、合成した得られたシュウ酸銀を濾過した後、洗浄、乾燥させることにより、熱安定性に優れたシュウ酸銀を作製することができる。 Thereafter, the synthesized silver oxalate is filtered, washed, and dried, whereby silver oxalate having excellent thermal stability can be produced.
次に、本発明の実施例及び比較例について説明する。なお、以下の実施例は、あくまで代表的な例を示しているもので、本発明はこれらの実施例に制限される必要はなく、明細書の記載される技術思想の範囲で解釈されるべきものである。 Next, examples and comparative examples of the present invention will be described. The following embodiments are merely representative examples, and the present invention is not limited to these embodiments and should be interpreted within the scope of the technical idea described in the specification. Things.
（実施例１）
２ｍｏｌ／Ｌの硝酸銀水溶液５００ｍｌに、０．８ｍｏｌ／Ｌのシュウ酸二水和物水溶液６２５ｍｌを滴下し、液温３０℃で混合し、３０分間、撹拌保持した。その後、これを濾過、洗浄した後、乾燥して、シュウ酸銀の結晶１５０ｇを得た。次に、得られたシュウ酸銀について、粉末Ｘ回折分析（ＸＲＤ）を行った。その結果を図１に示す。また熱重量分析（ＴＧ）及び示差熱分析（ＤＴＡ）についても行った。以上の結果をまとめたものを表１に示す。表１に示す通り、実施例１のシュウ酸銀は、特有の結晶構造を有し、熱安定性に優れたものであった。(Example 1)
625 ml of a 0.8 mol / L oxalic acid dihydrate aqueous solution was added dropwise to 500 ml of a 2 mol / L silver nitrate aqueous solution, mixed at a liquid temperature of 30 ° C., and stirred and maintained for 30 minutes. Thereafter, this was filtered, washed, and dried to obtain 150 g of silver oxalate crystals. Next, the obtained silver oxalate was subjected to powder X-ray diffraction analysis (XRD). The result is shown in FIG. Thermogravimetric analysis (TG) and differential thermal analysis (DTA) were also performed. Table 1 summarizes the above results. As shown in Table 1, the silver oxalate of Example 1 had a unique crystal structure and was excellent in thermal stability.
（実施例２）
１ｍｏｌ／Ｌの硝酸銀水溶液１０００ｍｌに、０．８ｍｏｌ／Ｌのシュウ酸二水和物水溶液６２５ｍｌを滴下し、液温３０℃で混合し、３０分間、撹拌保持した。その後、これを濾過、洗浄した後、乾燥して、シュウ酸銀の結晶１５０ｇを得た。得られたシュウ酸銀について、粉末Ｘ回折分析（ＸＲＤ）を行った。その結果を図１に示す。また、熱重量分析（ＴＧ）及び示差熱分析（ＤＴＡ）についても行った。以上の結果をまとめたものを表１に示す。表１に示す通り、実施例２のシュウ酸銀は、特有の結晶構造を有し、熱安定性に優れたものであった。(Example 2)
625 ml of a 0.8 mol / L oxalic acid dihydrate aqueous solution was dropped into 1000 ml of a 1 mol / L silver nitrate aqueous solution, mixed at a liquid temperature of 30 ° C., and stirred and maintained for 30 minutes. Thereafter, this was filtered, washed, and dried to obtain 150 g of silver oxalate crystals. The obtained silver oxalate was subjected to powder X-ray diffraction analysis (XRD). The result is shown in FIG. In addition, thermogravimetric analysis (TG) and differential thermal analysis (DTA) were also performed. Table 1 summarizes the above results. As shown in Table 1, the silver oxalate of Example 2 had a unique crystal structure and was excellent in thermal stability.
（実施例３）
０．７５ｍｏｌ／Ｌの硝酸銀水溶液１３３３ｍｌに、０．８ｍｏｌ／Ｌのシュウ酸二水和物水溶液６２５ｍｌを滴下し、液温３０℃で混合し、３０分間、撹拌保持した。その後これを濾過、洗浄した後、乾燥して、シュウ酸銀の結晶１５０ｇを得た。得られたシュウ酸銀について、粉末Ｘ回折分析（ＸＲＤ）を行った。その結果を図１に示す。また、熱重量分析（ＴＧ）及び示差熱分析（ＤＴＡ）についても行った。以上の結果をまとめたものを表１に示す。表１に示す通り、実施例３のシュウ酸銀は、特有の結晶構造を有し熱安定性に優れたものであった。(Example 3)
To 1333 ml of a 0.75 mol / L silver nitrate aqueous solution, 625 ml of a 0.8 mol / L oxalic acid dihydrate aqueous solution was dropped, mixed at a liquid temperature of 30 ° C., and kept under stirring for 30 minutes. Thereafter, this was filtered, washed, and dried to obtain 150 g of silver oxalate crystals. The obtained silver oxalate was subjected to powder X-ray diffraction analysis (XRD). The result is shown in FIG. In addition, thermogravimetric analysis (TG) and differential thermal analysis (DTA) were also performed. Table 1 summarizes the above results. As shown in Table 1, the silver oxalate of Example 3 had a unique crystal structure and was excellent in thermal stability.
（実施例４）
０．７５ｍｏｌ／Ｌの硝酸銀水溶液１３３３ｍｌに、０．５ｍｏｌ／Ｌのシュウ酸二水和物水溶液１０００ｍｌを滴下し、液温３０℃で混合し、３０分間、撹拌保持した。その後これを濾過、洗浄した後、乾燥して、シュウ酸銀の結晶１５０ｇを得た。得られたシュウ酸銀について、粉末Ｘ回折分析（ＸＲＤ）を行った。その結果を図１に示す。また、熱重量分析（ＴＧ）及び示差熱分析（ＤＴＡ）についても行った。以上の結果をまとめたものを表１に示す。表１に示す通り、実施例４のシュウ酸銀は、特有の結晶構造を有し熱安定性に優れたものであった。(Example 4)
To 1333 ml of a 0.75 mol / L silver nitrate aqueous solution, 1000 ml of a 0.5 mol / L oxalic acid dihydrate aqueous solution was dropped, mixed at a liquid temperature of 30 ° C., and stirred and maintained for 30 minutes. Thereafter, this was filtered, washed, and dried to obtain 150 g of silver oxalate crystals. The obtained silver oxalate was subjected to powder X-ray diffraction analysis (XRD). The result is shown in FIG. In addition, thermogravimetric analysis (TG) and differential thermal analysis (DTA) were also performed. Table 1 summarizes the above results. As shown in Table 1, the silver oxalate of Example 4 had a unique crystal structure and was excellent in thermal stability.
（実施例５）
２ｍｏｌ／Ｌの硝酸銀水溶液５００ｍｌに、０．８ｍｏｌ／Ｌのシュウ酸二水和物水溶液６２５ｍｌを滴下し、液温３０℃で混合し、２４時間、撹拌保持した。その後、これを濾過、洗浄した後、乾燥して、シュウ酸銀の結晶１５０ｇを得た。次に、得られたシュウ酸銀について、粉末Ｘ回折分析（ＸＲＤ）を行った。その結果を図１に示す。また熱重量分析（ＴＧ）及び示差熱分析（ＤＴＡ）についても行った。以上の結果をまとめたものを表１に示す。表１に示す通り、実施例５のシュウ酸銀は、特有の結晶構造を有し、熱安定性に優れたものであった。(Example 5)
625 ml of a 0.8 mol / L oxalic acid dihydrate aqueous solution was added dropwise to 500 ml of a 2 mol / L silver nitrate aqueous solution, mixed at a liquid temperature of 30 ° C., and stirred and maintained for 24 hours. Thereafter, this was filtered, washed, and dried to obtain 150 g of silver oxalate crystals. Next, the obtained silver oxalate was subjected to powder X-ray diffraction analysis (XRD). The result is shown in FIG. Thermogravimetric analysis (TG) and differential thermal analysis (DTA) were also performed. Table 1 summarizes the above results. As shown in Table 1, the silver oxalate of Example 5 had a unique crystal structure and was excellent in thermal stability.
（実施例６）
２ｍｏｌ／Ｌの硝酸銀水溶液５００ｍｌに、０．８ｍｏｌ／Ｌのシュウ酸二水和物水溶液６２５ｍｌを滴下し、液温４０℃で混合し、４時間、撹拌保持した。その後、これを濾過、洗浄した後、乾燥して、シュウ酸銀の結晶１５０ｇを得た。次に、得られたシュウ酸銀について、粉末Ｘ回折分析（ＸＲＤ）を行った。その結果を図１に示す。また熱重量分析（ＴＧ）及び示差熱分析（ＤＴＡ）についても行った。以上の結果をまとめたものを表１に示す。表１に示す通り、実施例６のシュウ酸銀は、特有の結晶構造を有し、熱安定性に優れたものであった。(Example 6)
625 ml of a 0.8 mol / L oxalic acid dihydrate aqueous solution was added dropwise to 500 ml of a 2 mol / L silver nitrate aqueous solution, mixed at a liquid temperature of 40 ° C., and kept under stirring for 4 hours. Thereafter, this was filtered, washed, and dried to obtain 150 g of silver oxalate crystals. Next, the obtained silver oxalate was subjected to powder X-ray diffraction analysis (XRD). The result is shown in FIG. Thermogravimetric analysis (TG) and differential thermal analysis (DTA) were also performed. Table 1 summarizes the above results. As shown in Table 1, the silver oxalate of Example 6 had a unique crystal structure and was excellent in thermal stability.
（比較例１）
０．５ｍｏｌ／Ｌの硝酸銀水溶液２０００ｍｌに、０．８ｍｏｌ／Ｌのシュウ酸二水和物水溶液６２５ｍｌを滴下し、液温３０℃で混合し、３０分間、撹拌保持した。その後これを濾過、洗浄した後、乾燥して、シュウ酸銀の結晶１５０ｇを得た。得られたシュウ酸銀について、粉末Ｘ回折分析（ＸＲＤ）を行った。その結果を図１に示す。また、熱重量分析（ＴＧ）及び示差熱分析（ＤＴＡ）についても行った。以上の結果をまとめたものを表１に示す。表１に示す通り、比較例１のシュウ酸銀は、実施例に比べて熱安定性に劣るものであった。(Comparative Example 1)
To 2,000 ml of a 0.5 mol / L silver nitrate aqueous solution, 625 ml of a 0.8 mol / L oxalic acid dihydrate aqueous solution was dropped, mixed at a liquid temperature of 30 ° C., and kept under stirring for 30 minutes. Thereafter, this was filtered, washed, and dried to obtain 150 g of silver oxalate crystals. The obtained silver oxalate was subjected to powder X-ray diffraction analysis (XRD). The result is shown in FIG. In addition, thermogravimetric analysis (TG) and differential thermal analysis (DTA) were also performed. Table 1 summarizes the above results. As shown in Table 1, the silver oxalate of Comparative Example 1 was inferior to the Examples in thermal stability.
（比較例２）
０．２５ｍｏｌ／Ｌの硝酸銀水溶液４０００ｍｌに、０．８ｍｏｌ／Ｌのシュウ酸二水和物水溶液６２５ｍｌを滴下し、液温３０℃で混合し、３０分間、撹拌保持した。その後これを濾過、洗浄した後、乾燥して、シュウ酸銀の結晶１５０ｇを得た。得られたシュウ酸銀について、粉末Ｘ回折分析（ＸＲＤ）を行った。その結果を図１に示す。また、熱重量分析（ＴＧ）及び示差熱分析（ＤＴＡ）についても行った。以上の結果をまとめたものを表１に示す。表１に示す通り、比較例２のシュウ酸銀は、実施例に比べて熱安定性に劣るものであった。(Comparative Example 2)
625 ml of a 0.8 mol / L oxalic acid dihydrate aqueous solution was dropped into 4000 ml of a 0.25 mol / L silver nitrate aqueous solution, mixed at a liquid temperature of 30 ° C., and stirred and maintained for 30 minutes. Thereafter, this was filtered, washed, and dried to obtain 150 g of silver oxalate crystals. The obtained silver oxalate was subjected to powder X-ray diffraction analysis (XRD). The result is shown in FIG. In addition, thermogravimetric analysis (TG) and differential thermal analysis (DTA) were also performed. Table 1 summarizes the above results. As shown in Table 1, the silver oxalate of Comparative Example 2 was inferior to the Examples in thermal stability.
（比較例３）
０．１ｍｏｌ／Ｌの硝酸銀水溶液１００００ｍｌに、０．８ｍｏｌ／Ｌのシュウ酸二水和物水溶液６２５ｍｌを滴下し、液温３０℃で混合し、３０分間、撹拌保持した。その後、これを濾過、洗浄した後、乾燥して、シュウ酸銀の結晶１５０ｇを得た。得られたシュウ酸銀について、粉末Ｘ回折分析（ＸＲＤ）を行った。その結果を図１に示す。また、熱重量分析（ＴＧ）及び示差熱分析（ＤＴＡ）についても行った。以上の結果をまとめたものを表１に示す。表１に示す通り、比較例３のシュウ酸銀は、実施例に比べて熱安定性に劣るものであった。(Comparative Example 3)
625 ml of a 0.8 mol / L oxalic acid dihydrate aqueous solution was dropped into 10,000 ml of a 0.1 mol / L silver nitrate aqueous solution, mixed at a liquid temperature of 30 ° C., and stirred and maintained for 30 minutes. Thereafter, this was filtered, washed, and dried to obtain 150 g of silver oxalate crystals. The obtained silver oxalate was subjected to powder X-ray diffraction analysis (XRD). The result is shown in FIG. In addition, thermogravimetric analysis (TG) and differential thermal analysis (DTA) were also performed. Table 1 summarizes the above results. As shown in Table 1, the silver oxalate of Comparative Example 3 was inferior to the Examples in thermal stability.
（比較例４）
２ｍｏｌ／Ｌの硝酸銀水溶液５００ｍｌに、０．８ｍｏｌ／Ｌのシュウ酸二水和物水溶液６２５ｍｌを滴下し、液温４０℃で混合し、８時間、撹拌保持した。その後、これを濾過、洗浄した後、乾燥して、シュウ酸銀の結晶１５０ｇを得た。次に、得られたシュウ酸銀について、粉末Ｘ回折分析（ＸＲＤ）を行った。その結果を図１に示す。また熱重量分析（ＴＧ）及び示差熱分析（ＤＴＡ）についても行った。以上の結果をまとめたものを表１に示す。表１に示す通り、比較例４のシュウ酸銀は、実施例に比べて熱安定性に劣るものであった。(Comparative Example 4)
625 ml of a 0.8 mol / L oxalic acid dihydrate aqueous solution was added dropwise to 500 ml of a 2 mol / L silver nitrate aqueous solution, mixed at a liquid temperature of 40 ° C., and stirred and maintained for 8 hours. Thereafter, this was filtered, washed, and dried to obtain 150 g of silver oxalate crystals. Next, the obtained silver oxalate was subjected to powder X-ray diffraction analysis (XRD). The result is shown in FIG. Thermogravimetric analysis (TG) and differential thermal analysis (DTA) were also performed. Table 1 summarizes the above results. As shown in Table 1, the silver oxalate of Comparative Example 4 was inferior to the Examples in thermal stability.
（比較例５）
２ｍｏｌ／Ｌの硝酸銀水溶液５００ｍｌに、０．８ｍｏｌ／Ｌのシュウ酸二水和物水溶液６２５ｍｌを滴下し、液温５０℃で混合し、４時間、撹拌保持した。その後、これを濾過、洗浄した後、乾燥して、シュウ酸銀の結晶１５０ｇを得た。次に、得られたシュウ酸銀について、粉末Ｘ回折分析（ＸＲＤ）を行った。その結果を図１に示す。また熱重量分析（ＴＧ）及び示差熱分析（ＤＴＡ）についても行った。以上の結果をまとめたものを表１に示す。表１に示す通り、比較例５のシュウ酸銀は、実施例に比べて熱安定性に劣るものであった。(Comparative Example 5)
625 ml of a 0.8 mol / L oxalic acid dihydrate aqueous solution was dropped into 500 ml of a 2 mol / L silver nitrate aqueous solution, mixed at a liquid temperature of 50 ° C., and stirred and maintained for 4 hours. Thereafter, this was filtered, washed, and dried to obtain 150 g of silver oxalate crystals. Next, the obtained silver oxalate was subjected to powder X-ray diffraction analysis (XRD). The result is shown in FIG. Thermogravimetric analysis (TG) and differential thermal analysis (DTA) were also performed. Table 1 summarizes the above results. As shown in Table 1, the silver oxalate of Comparative Example 5 was inferior to the examples in heat stability.
本発明の実施形態によれば、熱安定性に優れたシュウ酸銀を製造することができる。シュウ酸銀は、銀ナノ粒子の製造における前駆体として有用であり、特に、銀ナノ粒子を用いた導電性ペーストや導電性インクに対して有用である。 According to the embodiment of the present invention, silver oxalate having excellent thermal stability can be produced. Silver oxalate is useful as a precursor in the production of silver nanoparticles, and is particularly useful for conductive pastes and conductive inks using silver nanoparticles.
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| JP2013016802A (en) * | 2011-06-30 | 2013-01-24 | Thales | Method of manufacturing device comprising braze produced from metal oxalate |
| JP2014529875A (en) * | 2011-09-06 | 2014-11-13 | ヘンケル アイピー アンド ホールディング ゲゼルシャフト ミット ベシュレンクテル ハフツング | Conductive materials and processes |
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| JP2013016802A (en) * | 2011-06-30 | 2013-01-24 | Thales | Method of manufacturing device comprising braze produced from metal oxalate |
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| CN102708943A (en) * | 2012-06-04 | 2012-10-03 | 惠州市富济电子材料有限公司 | Low-temperature sintered highly-heat-conductive and highly-electric-conductive silver paste, preparation method and sintering method |
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