JP4706835B2 - Method for producing gold fine particles - Google Patents
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- 239000010931 gold Substances 0.000 title claims description 97
- 229910052737 gold Inorganic materials 0.000 title claims description 97
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 title claims description 86
- 239000010419 fine particle Substances 0.000 title claims description 37
- 238000004519 manufacturing process Methods 0.000 title claims description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 42
- 239000002245 particle Substances 0.000 claims description 40
- 239000000243 solution Substances 0.000 claims description 34
- 239000002253 acid Substances 0.000 claims description 24
- AKXUUJCMWZFYMV-UHFFFAOYSA-M tetrakis(hydroxymethyl)phosphanium;chloride Chemical compound [Cl-].OC[P+](CO)(CO)CO AKXUUJCMWZFYMV-UHFFFAOYSA-M 0.000 claims description 23
- -1 gold ion Chemical class 0.000 claims description 19
- 239000003638 chemical reducing agent Substances 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- 230000001603 reducing effect Effects 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 6
- 239000012670 alkaline solution Substances 0.000 claims description 3
- YTVQIZRDLKWECQ-UHFFFAOYSA-N 2-benzoylcyclohexan-1-one Chemical compound C=1C=CC=CC=1C(=O)C1CCCCC1=O YTVQIZRDLKWECQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 description 31
- 239000002105 nanoparticle Substances 0.000 description 27
- 239000000463 material Substances 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 230000003287 optical effect Effects 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 4
- 238000010304 firing Methods 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000012279 sodium borohydride Substances 0.000 description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 150000002343 gold Chemical class 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000003223 protective agent Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- QBVXKDJEZKEASM-UHFFFAOYSA-M tetraoctylammonium bromide Chemical compound [Br-].CCCCCCCC[N+](CCCCCCCC)(CCCCCCCC)CCCCCCCC QBVXKDJEZKEASM-UHFFFAOYSA-M 0.000 description 1
Description
本発明は、電子部品の配線材料、色材、光学フィルター、触媒などに用いられるナノサイズの金微粒子（金ナノ粒子と云うことがある）の製造方法に関する。
The present invention relates to a method for producing nano-sized gold fine particles (sometimes referred to as gold nanoparticles) used for wiring materials, color materials, optical filters, catalysts and the like of electronic components.
従来、金ナノ粒子は金イオンを含む溶液に還元液を添加して金イオンを還元する液相還元法によって主に製造されている。例えば、塩化金酸水溶液に還元剤溶液（水素化ホウ素ナトリウム溶液）を添加して金イオンを還元し、さらに、水と相溶しない有機溶媒に分散させた保護剤溶液（１−オクタンチオールヘキサン溶液）を添加して攪拌し、有機溶媒中に金微粒子を抽出する方法が知られている（特許文献１、特許文献２）。しかし、これらの方法によって製造される金微粒子の平均粒子径は何れも３ｎｍより大きい。 Conventionally, gold nanoparticles are mainly produced by a liquid phase reduction method in which a reducing solution is added to a solution containing gold ions to reduce the gold ions. For example, a reducing agent solution (sodium borohydride solution) is added to a chloroauric acid aqueous solution to reduce gold ions, and further a protective agent solution (1-octanethiol hexane solution) dispersed in an organic solvent incompatible with water. ) Is added and stirred to extract gold fine particles in an organic solvent (Patent Documents 1 and 2). However, the average particle diameter of the gold fine particles produced by these methods is larger than 3 nm.
また、塩化金酸水溶液にトルエンと界面活性剤（ＴＯＡＢ等）を加えて攪拌し、塩化金酸をトルエンに抽出した後に還元剤溶液（水素化ホウ素ナトリウム溶液）を加え、固形分を回収して加熱処理し、冷却後に固形物をトルエンに再溶解し、この沈澱物を濾過して金微粒子を得る製造方法が知られている（特許文献３）。しかし、この方法によって得られる金微粒子の平均粒子径もまた３ｎｍより大きい。 In addition, toluene and a surfactant (TOAB, etc.) are added to an aqueous chloroauric acid solution and stirred. After extracting chloroauric acid into toluene, a reducing agent solution (sodium borohydride solution) is added to recover the solid content. A manufacturing method is known in which a solid is redissolved in toluene after heat treatment and cooled, and the precipitate is filtered to obtain gold fine particles (Patent Document 3). However, the average particle size of the gold fine particles obtained by this method is also larger than 3 nm.
また、水酸化ナトリウム水溶液とＴＨＰＣ水溶液を予め混合した後に、この混合液に塩化金酸水溶液を混合して金コロイドを得る方法が知られている（特許文献４）。しかし、この製造方法では、金濃度が０.１mol/l以上になると、生成する金微粒子の粒子径が４ｎｍ以上になる。金濃度が０.００１mol/l程度の薄い塩化金酸水溶液を用いれば、粒子径３ｎｍ以下の金微粒子を製造することができるが、濃度が極端に薄いため十分な収量を得ることができず、工業レベルでの実用化に適さない。
本発明は、従来の製造方法の上記問題を解決したものであり、金イオン溶液の金濃度が高くても平均粒子径３ｎｍ以下の金微粒子を十分な収量で得ることができる製造方法を提供するものであり、また、この方法によって製造された粒子径の変動係数と比抵抗率の小さい金ナノ粒子を提供するものである。 The present invention solves the above-mentioned problems of the conventional production method, and provides a production method capable of obtaining gold fine particles having an average particle diameter of 3 nm or less with a sufficient yield even when the gold concentration of the gold ion solution is high. In addition, the present invention provides gold nanoparticles having a small coefficient of variation in particle diameter and a small specific resistance produced by this method.
本発明は以下の金ナノ粒子の製造方法に関する。
〔１〕金イオン溶液に還元剤溶液を混合して金微粒子を製造する方法において、還元剤としてテトラキス(ヒドロキシメチル)ホスホニウムクロリド（以下、ＴＨＰＣと云う）を用い、金イオン溶液と還元剤溶液を混合した後に、この混合溶液をアルカリ溶液に添加して金イオンを還元することによって平均粒子径３ｎｍ以下であって粒子径の変動係数が２０％以下である金微粒子を製造することを特徴とする方法。
〔２〕塩化金酸水溶液にＴＨＰＣ水溶液を混合し、この混合溶液を水酸化ナトリウム水溶液に添加して金微粒子を製造する方法であって、塩化金酸水溶液の金濃度が０.０２５〜２.５mol/l、ＴＨＰＣ量が金濃度の１〜４モル倍、水酸化ナトリウム量が金濃度の７〜１５モル倍である上記[１]に記載する金微粒子の製造方法。
The present invention relates to the following method for producing gold nanoparticles.
[1] In a method for producing a gold fine particle by mixing a reducing agent solution with a gold ion solution, tetrakis (hydroxymethyl) phosphonium chloride (hereinafter referred to as THPC) is used as the reducing agent, and the gold ion solution and the reducing agent solution are mixed. After mixing, this mixed solution is added to an alkaline solution to reduce gold ions, thereby producing gold fine particles having an average particle size of 3 nm or less and a particle size variation coefficient of 20% or less. Method.
[2] A method in which a THPC aqueous solution is mixed with an aqueous chloroauric acid solution, and this mixed solution is added to an aqueous sodium hydroxide solution to produce gold fine particles. The gold concentration of the aqueous chloroauric acid solution is 0.025 to 2. The method for producing gold fine particles according to the above [1], wherein 5 mol / l, THPC amount is 1 to 4 mol times the gold concentration, and sodium hydroxide amount is 7 to 15 mol times the gold concentration.
〔具体的な説明〕
本発明の製造方法に係る金ナノ粒子は、平均粒子径３ｎｍ以下であって、粒子径の変動係数が２０％以下の金微粒子である。本発明の金ナノ粒子は、金イオン溶液に還元剤溶液を混合して金微粒子を製造する方法において、アルカリ域で作用する還元剤の溶液と金イオン溶液とを予め混合した後に、この混合溶液にアルカリ溶液を混合して金イオンを還元することによって得ることができる。
[Specific description]
The gold nanoparticles according to the production method of the present invention are fine gold particles having an average particle diameter of 3 nm or less and a coefficient of variation of the particle diameter of 20% or less. In the method for producing gold fine particles by mixing a reducing agent solution into a gold ion solution, the gold nanoparticle of the present invention is prepared by previously mixing a solution of a reducing agent acting in an alkaline region and a gold ion solution. It can be obtained by mixing an alkaline solution and reducing gold ions.
具体的には、本発明の金ナノ粒子は、塩化金酸水溶液とＴＨＰＣ水溶液を混合し、この混合水溶液を水酸化ナトリウム水溶液と混合して金イオンを還元することによって得ることができる。 Specifically, the gold nanoparticles of the present invention can be obtained by mixing a chloroauric acid aqueous solution and a THPC aqueous solution, mixing the mixed aqueous solution with a sodium hydroxide aqueous solution, and reducing gold ions.
還元剤のＴＨＰＣは強アルカリ域で急速に作用するので、従来の製造方法では、予めＴＨＰＣ水溶液を水酸化ナトリウム水溶液と混合し、強アルカリ性のＴＨＰＣ水溶液とし、これと塩化金酸水溶液とを混合して塩化金酸を還元している。しかし、このように強アルカリ性のＴＨＰＣ水溶液を予め形成し、これと塩化金酸水溶液とを混合すると、塩化金酸の還元が急激に進行し、例えば、局所的に生成した金微粒子を核とし、周囲の金イオンが還元されてこの金微粒子の成長に費やされ、局所的に粒径の大きな金微粒子になるため、平均粒子径３ｎｍ以下の金ナノ粒子が生成し難い。 Since the reducing agent THPC acts rapidly in a strong alkali region, in the conventional production method, a THPC aqueous solution is mixed with a sodium hydroxide aqueous solution in advance to form a strong alkaline THPC aqueous solution, which is mixed with a chloroauric acid aqueous solution. Reducing chloroauric acid. However, when a strong alkaline THPC aqueous solution is formed in advance and this is mixed with a chloroauric acid aqueous solution, the reduction of chloroauric acid proceeds rapidly. For example, locally generated gold fine particles are used as nuclei, Since the surrounding gold ions are reduced and consumed for the growth of the gold fine particles, and locally become gold fine particles having a large particle diameter, it is difficult to produce gold nanoparticles having an average particle diameter of 3 nm or less.
一方、本発明の製造方法は、水酸化ナトリウム水溶液を加えずにＴＨＰＣ水溶液を塩化金酸水溶液と混合する。このように、ＴＨＰＣの還元力が実質的に未だ作用しない状態で塩化金酸と混合することによって、ＴＨＰＣと塩化金酸とを均一に混合し、急激な還元作用による局部的な金微粒子の生成を抑制する。次いで、この混合水溶液に水酸化ナトリウム水溶液を添加して強アルカリ性に転化し、ＴＨＰＣの還元作用を発揮させる。このような方法によって、塩化金酸が液中で均一に還元され、金微粒子の成長が局部的に進行することがないので、平均粒子径３ｎｍ以下の金ナノ粒子を高い収率で得ることができる。 On the other hand, in the production method of the present invention, the THPC aqueous solution is mixed with the chloroauric acid aqueous solution without adding the sodium hydroxide aqueous solution. In this way, THPC and chloroauric acid are uniformly mixed by mixing with chloroauric acid in a state where the reducing power of THPC does not substantially act yet, and local gold fine particles are generated by abrupt reduction action. Suppress. Next, an aqueous sodium hydroxide solution is added to the mixed aqueous solution to convert it into a strong alkalinity, thereby exhibiting the reducing action of THPC. By such a method, since chloroauric acid is uniformly reduced in the liquid and the growth of gold fine particles does not proceed locally, gold nanoparticles having an average particle diameter of 3 nm or less can be obtained in a high yield. it can.
具体的には、例えば、塩化金酸水溶液の金濃度０.０２５〜２.５mol/lにおいて、ＴＨＰＣ量を金濃度の１〜４モル倍、水酸化ナトリウム量を金濃度の７〜１５モル倍とし、５〜６０分間混合した後に、還元剤のＴＨＰＣを除去することによって、粒子径３ｎｍ以下の微細な金ナノ粒子を８５％以上の収率で得ることができる。なお、ＴＨＰＣを除去するには、生成した金ナノ粒子を含む反応液を遠心分離して金ナノ粒子を回収し、または非水系溶剤などに金ナノ粒子を抽出するなどの方法によれば良い。 Specifically, for example, when the gold concentration of the chloroauric acid aqueous solution is 0.025 to 2.5 mol / l, the THPC amount is 1 to 4 mol times the gold concentration, and the sodium hydroxide amount is 7 to 15 mol times the gold concentration. Then, after mixing for 5 to 60 minutes, by removing the reducing agent THPC, fine gold nanoparticles having a particle diameter of 3 nm or less can be obtained in a yield of 85% or more. In order to remove THPC, the reaction solution containing the generated gold nanoparticles may be centrifuged to collect the gold nanoparticles, or the gold nanoparticles may be extracted into a non-aqueous solvent or the like.
本発明の方法によって製造した金ナノ粒子は、粒子径の変動係数（相対標準偏差）が２０％以下であり、粒子径の均一な金ナノ粒子を得ることができる。 The gold nanoparticles produced by the method of the present invention have a particle diameter variation coefficient (relative standard deviation) of 20% or less, and gold nanoparticles having a uniform particle diameter can be obtained.
本発明の製造方法に係る金ナノ粒子は、平均粒子径３ｎｍ以下、例えば平均粒子径１〜３ｎｍであり、粒子径の変動係数が２０％以下の均一な微粒子であるので、これを配線材料、色材、光学フィルター、触媒などの機能性材料として均質な性能を得ることができる。さらに、この金微粒子を含む膜は、低い加熱焼成温度（３００℃以下）でも比抵抗率が小さいので、特に高温加熱が困難な導電材料に適する。
Since the gold nanoparticles according to the production method of the present invention are uniform fine particles having an average particle diameter of 3 nm or less, for example, an average particle diameter of 1 to 3 nm and a coefficient of variation of the particle diameter of 20% or less, Homogeneous performance can be obtained as functional materials such as coloring materials, optical filters, and catalysts. Further, the film containing the gold fine particles has a small specific resistance even at a low heating and baking temperature (300 ° C. or lower), and is therefore suitable for a conductive material that is difficult to heat at high temperatures.
具体的には、例えば、ディスプレイなどの表面から発生する人体に有害な電磁波をシールドするために、その表面にＩＴＯなどの導電性の膜が設けられている。この導電性膜には比抵抗率が小さく、かつ高い透明度が要求される。しかし、ＩＴＯなどで十分な導電性を得るためには十分な膜厚が必要になり、コストが高い。本発明の金ナノ粒子は平均粒子径３ｎｍ以下の微細粒子であるので高い透明性を有し、かつ導電性に優れているので、電磁波シールド膜などの材料に適する。 Specifically, for example, in order to shield an electromagnetic wave harmful to the human body generated from the surface of a display or the like, a conductive film such as ITO is provided on the surface. This conductive film is required to have a low specific resistivity and high transparency. However, in order to obtain sufficient conductivity with ITO or the like, a sufficient film thickness is required, and the cost is high. Since the gold nanoparticles of the present invention are fine particles having an average particle diameter of 3 nm or less, they have high transparency and are excellent in conductivity, and are therefore suitable for materials such as an electromagnetic shielding film.
また、従来の金粒子は触媒活性が乏しいので触媒として利用されていないが、本発明の金ナノ粒子は平均粒子径を３ｎｍ以下にすることによって表面エネルギーが大きく、高い活性を有するので触媒として利用することができる。 In addition, conventional gold particles are not used as a catalyst because of their poor catalytic activity, but the gold nanoparticles of the present invention have a high surface energy and high activity when the average particle size is 3 nm or less, so they are used as a catalyst. can do.
また、配線材料として金微粒子を焼結して用いるが、従来の方法によって製造した金微粒子の焼結体に比べて、本発明の金ナノ粒子焼結体の比抵抗率は大幅に小さく、配線材料として有利である。具体的には、金微粒子を含むペーストを配線材料として用いる場合、このペーストを印刷した後に焼結して配線を形成するが、従来の液相還元法によって製造した金粒子は概ね直径５ｎｍ以上であり、これを配線材料として用いるには比較的高い温度で焼結しなければならない。一方、本発明に係る金ナノ粒子は平均粒子径３ｎｍ以下にすることによって表面エネルギーが大きくなるので、従来の焼成温度よりも低温での焼成が可能であり、比抵抗を格段に小さくすることができる。具体的には、本発明の金微粒子を配合し、焼成してなる被膜において、比抵抗率１×１０-4Ω・cm以下の導電性に優れた被膜を得ることができる。因みに、表１に示すように、従来の金粒子を２００〜３００℃で１５〜３０分間焼成したときの比抵抗率は概ね２３.０×１０-5〜３４０.０×１０-5Ω・cmであるが、本発明の金ナノ粒子は、同様の焼成条件において、２.３×１０-5〜４.０×１０-5Ω・cmであり、従来の約１／１０〜１／１５０であって比抵抗率が格段に小さい。 In addition, gold fine particles are sintered and used as a wiring material, but the specific resistivity of the gold nanoparticle sintered body of the present invention is significantly smaller than that of a sintered gold fine particle produced by a conventional method. It is advantageous as a material. Specifically, when a paste containing gold fine particles is used as a wiring material, the paste is printed and then sintered to form a wiring. Gold particles produced by a conventional liquid phase reduction method generally have a diameter of 5 nm or more. In order to use it as a wiring material, it must be sintered at a relatively high temperature. On the other hand, since the surface energy of the gold nanoparticles according to the present invention is increased by making the average particle diameter 3 nm or less, firing can be performed at a temperature lower than the conventional firing temperature, and the specific resistance can be significantly reduced. it can. Specifically, in a film formed by blending and firing the gold fine particles of the present invention, a film having a specific resistivity of 1 × 10 −4 Ω · cm or less and excellent conductivity can be obtained. Incidentally, as shown in Table 1, the specific resistivity when the conventional gold particles are baked at 200 to 300 ° C. for 15 to 30 minutes is approximately 23.0 × 10 −5 to 340.0 × 10 −5 Ω · cm. However, the gold nanoparticles of the present invention are 2.3 × 10 −5 to 4.0 × 10 −5 Ω · cm under the same firing conditions, which is about 1/10 to 1/150 of the conventional one. And the specific resistivity is much smaller.
金コロイドなどの金粒子が分散した系では、粒子径に応じて紫、青、赤などの色を発色する。この発色はプラズモン吸収と呼ばれ、電子のプラズマ振動に起因する。プラズモン吸収が大きいとディスプレイの発色を阻害する。本発明の金ナノ粒子は平均粒径を３ｎｍ以下にすることによって、光吸収スペクトルにおいて５２０ｎｍ近傍のプラズモン吸収を小さくし、あるいは実質的に生じないようにした。この本発明の金ナノ粒子を用いれば、可視光域においてディスプレイの発色を阻害しない良好な光学フィルターを得ることができる。 In a system in which gold particles such as gold colloid are dispersed, colors such as purple, blue and red are developed according to the particle diameter. This color development is called plasmon absorption and is caused by electron plasma oscillation. If the plasmon absorption is large, the color development of the display is inhibited. The gold nanoparticles of the present invention have an average particle size of 3 nm or less, thereby reducing or substantially preventing plasmon absorption near 520 nm in the light absorption spectrum. By using this gold nanoparticle of the present invention, it is possible to obtain a good optical filter that does not inhibit display color development in the visible light region.
また、本発明の製造方法は、原料の金イオン濃度が０.１mol/l程度でも平均粒子径３ｎｍ以下の金ナノ粒子を容易に得ることができるので、工業的実施に適する。 Further, the production method of the present invention is suitable for industrial implementation because gold nanoparticles having an average particle diameter of 3 nm or less can be easily obtained even when the concentration of gold ions in the raw material is about 0.1 mol / l.
本発明の金微粒子は非常に微細であり、かつ粒子径が均一であるので、この金微粒子を含むペースト、コロイドを用いれば、光学特性に優れた被膜や光学フィルター材料を得ることができる。また、この金微粒子は、従来のものより微粒子であるので焼結温度が低く、従って、焼結温度以上で焼成して形成した被膜や光学フィルター材料なども光学特性に優れたものを得ることができる。 Since the gold fine particles of the present invention are very fine and have a uniform particle size, a coating or optical filter material having excellent optical properties can be obtained by using a paste or colloid containing the gold fine particles. Further, since the gold fine particles are finer than the conventional fine particles, the sintering temperature is lower, and therefore, a film formed by baking at a temperature higher than the sintering temperature, an optical filter material, etc. can be obtained with excellent optical characteristics. it can.
以下、本発明の実施例を示す。結果を表１に示した。
〔実施例１〕
ＴＨＰＣ水溶液（濃度２.５mol/l）３mlと塩化金酸水溶液（濃度２.５mol/l）２mlとを混合した溶液を、水酸化ナトリウム水溶液（濃度１０mol/l）５mlに純水４０mlを加えて希釈した水溶液に加えて５分間攪拌し混合した。この混合溶液を遠心分離して金コロイドを回収した。この金コロイドは平均粒子径３ｎｍ以下であり、３ｎｍ以下の金微粒子の収量９１０ｍｇ（収率９１％）であった。また、粒子径の変動係数は１６％、３００℃で１５分〜３０分焼成したときの比抵抗率は２.５×１０-5〜３.５×１０-5Ω・cmであった（表１No.１）。
Examples of the present invention will be described below. The results are shown in Table 1.
[Example 1]
A mixed solution of 3 ml of THPC aqueous solution (concentration 2.5 mol / l) and 2 ml of chloroauric acid aqueous solution (concentration 2.5 mol / l) was added to 40 ml of pure water to 5 ml of sodium hydroxide aqueous solution (concentration 10 mol / l). In addition to the diluted aqueous solution, the mixture was stirred for 5 minutes and mixed. The mixed solution was centrifuged to recover the colloidal gold. This gold colloid had an average particle diameter of 3 nm or less, and the yield of gold fine particles of 3 nm or less was 910 mg (yield 91%). The coefficient of variation of the particle diameter was 16%, and the specific resistivity when fired at 300 ° C. for 15 to 30 minutes was 2.5 × 10 −5 to 3.5 × 10 −5 Ω · cm (Table) 1 No. 1).
〔実施例２〜５〕
ＴＨＰＣ水溶液、塩化金酸水溶液、水酸化ナトリウム水溶液について、表１に示す濃度および使用量を用いて金コロイドを製造した。また、実施例１と同一条件で焼成したときの比抵抗率を測定した。この結果を表１に示した（No.2〜No.5）。
[Examples 2 to 5]
Colloidal gold was produced using the concentrations and amounts used in Table 1 for the THPC aqueous solution, chloroauric acid aqueous solution, and sodium hydroxide aqueous solution. Moreover, the specific resistivity when baked on the same conditions as Example 1 was measured. The results are shown in Table 1 (No. 2 to No. 5).
〔比較例〕
ＴＨＰＣ水溶液、塩化金酸水溶液、水酸化ナトリウム水溶液について、表１に示す濃度および使用量を用い、あらかじめＴＨＰＣ水溶液と水酸化ナトリウム水溶液を混合した溶液に塩化金酸水溶液を添加して金コロイドを製造した。また、実施例１と同一条件で焼成したときの比抵抗率を測定した。この結果を表１に示したこの結果を表１に示した（No.6〜No.8）。
[Comparative example]
For the THPC aqueous solution, chloroauric acid aqueous solution, and sodium hydroxide aqueous solution, gold colloid is produced by adding the chloroauric acid aqueous solution to the solution in which the THPC aqueous solution and the sodium hydroxide aqueous solution are mixed in advance using the concentrations and usage amounts shown in Table 1. did. Moreover, the specific resistivity when baked on the same conditions as Example 1 was measured. The results are shown in Table 1. The results are shown in Table 1 (No. 6 to No. 8).
本発明の実施例では、金濃度０.２５mol/l〜２.５mol/lにおいて、平均粒子径３ｎｍ以下の金ナノ粒子が８７％以上の高収率で製造される。一方、比較例では、得られる金微粒子の平均粒子径は３ｎｍ以上であり、平均粒子径３ｎｍ以下の微細な金ナノ粒子の収率は、金濃度２.５mol/lでは３６％以下と低く、金濃度０.２５mol/lの薄い塩化金酸溶液を用いた場合でも６５％であり、結局、平均粒子径３ｎｍ以下であって粒子径の変動係数２０％以下の金微粒子を得ることはできない。 In the examples of the present invention, gold nanoparticles having an average particle diameter of 3 nm or less are produced in a high yield of 87% or more at a gold concentration of 0.25 mol / l to 2.5 mol / l. On the other hand, in the comparative example, the average particle diameter of the obtained gold fine particles is 3 nm or more, and the yield of fine gold nanoparticles having an average particle diameter of 3 nm or less is as low as 36% or less at a gold concentration of 2.5 mol / l. Even when a thin chloroauric acid solution having a gold concentration of 0.25 mol / l is used, it is 65%. As a result, it is impossible to obtain gold fine particles having an average particle diameter of 3 nm or less and a coefficient of variation of particle diameter of 20% or less.
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