JP5063003B2 - Method for producing copper nanoparticles, copper nanoparticles, conductive composition, and electronic device - Google Patents
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Description
本発明は銅ナノ粒子の製造方法、銅ナノ粒子、導電性組成物および電子デバイスに関し、詳しくは銅ナノ粒子の製造方法、この方法によって得られる銅ナノ粒子、ならびにこの銅ナノ粒子を含有する導電性組成物およびこの導電性組成物を用いて形成した被膜層を有する電子デバイスに関する。 Production method of the present invention is copper nanoparticles, copper nanoparticles, relates conductive composition and electronic devices, and more particularly a method of manufacturing a copper nanoparticles, copper nanoparticles obtained by this method, as well as conductive containing the copper nano-particles The present invention relates to a conductive composition and an electronic device having a coating layer formed using the conductive composition.
有機酸金属塩とアミン化合物とを反応させて金属微粒子を製造し、この金属微粒子を用いて導電性被覆層を形成することはよく知られているところであり、既に多くの方法が提案されている。例えば、特許文献１には、このような導電性被覆層を形成するに好適なものとされる金属元素含有有機化合物ペースト、およびこのペーストを用いて得られる電子デバイスが提案されている。 It is well known to produce metal fine particles by reacting an organic acid metal salt and an amine compound, and to form a conductive coating layer using the metal fine particles, and many methods have already been proposed. . For example, Patent Document 1 proposes a metal element-containing organic compound paste that is suitable for forming such a conductive coating layer, and an electronic device obtained using this paste.
特許文献１に記載の方法によって得られる金属微粒子は、粒子径が０．１μｍ（１００ｎｍ）以下とされているが、その粒度分布についての記載はない。しかし、例えば、導電パターン描画用インク組成物として、導電性被覆層を形成する場合、平均粒子径が１０ｎｍを超え、しかも粒子径が均一でなく、粒度分布が広い金属微粒子を用いると、金属微粒子の分散体であるインクの保管時に凝集が生じやすくなり、その結果、インクジェット装置を用いて回路パターンを描画する際につまりなどの問題が生じる可能性がある。さらに、導電性の金属膜を焼成処理などにより形成する場合、粒子間の空隙が大きくなるため、均一な膜の形成が難しくなることや基板との密着性が低くなるなどの問題が生じる。 The metal fine particles obtained by the method described in Patent Document 1 have a particle size of 0.1 μm (100 nm) or less, but there is no description of the particle size distribution. However, for example, when forming a conductive coating layer as an ink composition for drawing a conductive pattern, if metal fine particles having an average particle diameter of more than 10 nm, a non-uniform particle diameter, and a wide particle size distribution are used, the metal fine particles Aggregation is likely to occur during storage of the ink, which is a dispersion of the ink, and as a result, problems such as clogging may occur when drawing a circuit pattern using an ink jet apparatus. Furthermore, when a conductive metal film is formed by firing or the like, voids between particles are increased, which causes problems such as difficulty in forming a uniform film and low adhesion to the substrate.
このように、従来の方法によって得られる金属微粒子は粒子径や粒子の均一性（粒度分布）などの点でなお不十分であり、更なる改善が望まれている。 As described above, the metal fine particles obtained by the conventional method are still insufficient in terms of the particle diameter and particle uniformity (particle size distribution), and further improvement is desired.
本発明の目的は、電子デバイスなどの導電性被覆層の形成に好適な粒子径や粒度分布などの特性を有する銅ナノ粒子およびそのような銅ナノ粒子の製造に好適な銅ナノ粒子の製造方法を提供することにある。また、本発明の目的は、上記銅ナノ粒子を含有する導電性組成物およびこの導電性組成物を用いて得られる被覆層を有する電子デバイスを提供することにある。 An object of the present invention, the production method of the preferred copper nanoparticles in the manufacture of copper nanoparticles and such copper nanoparticles having properties such as a suitable particle size and particle size distribution in the formation of conductive coating layer, such as an electronic device Is to provide. Moreover, the objective of this invention is providing the electronic device which has a coating layer obtained using the electroconductive composition containing the said copper nanoparticle, and this electroconductive composition.
本発明者らの研究によれば、前記課題は下記発明により達成できることがわかった。
（１）攪拌機付き反応装置内で有機酸銅塩と炭素数８〜１６のモノアミン化合物とを含む溶液に還元剤を添加し、銅金属核の形成およびその成長を行わせて銅ナノ粒子を製造する方法であって、該銅金属核の形成およびその成長を１０〜５５℃の温度、かつ、還元剤を添加するときの液温変化ΔＴが２０℃以下の条件下で行うことを特徴とする銅ナノ粒子の製造方法。
（２）有機酸銅塩がギ酸銅、酢酸銅、シュウ酸銅、オレイン酸銅、ステアリン酸銅およびテトラデカン酸銅から選ばれる少なくとも１種である上記（１）の銅ナノ粒子の製造方法。
（３）炭素数８〜１６のモノアミン化合物がオクチルアミン、ノニルアミン、デシルアミン、ウンデシルアミン、ドデシルアミン、トリデシルアミン、テトラデシルアミン、ペンタデシルアミン、ヘキサデシルアミン、ドデシルジメチルアミンおよびトリオクチルアミンから選ばれる少なくとも１種である上記（１）または（２）の銅ナノ粒子の製造方法。
（４）還元剤がジメチルアミンボラン、ｔｅｒｔ−ブチルアミンボラン、水素化ホウ素ナトリウム、シュウ酸、アスコルビン酸、ホルムアルデヒドおよびアセトアルデヒドから選ばれる少なくとも１種である上記（１）〜（３）のいずれかの銅ナノ粒子の製造方法。
（５）上記（１）〜（４）のいずれかの銅ナノ粒子の製造方法により調製した、平均粒子径（Ｄ）が１０ｎｍ以下であり、かつσ／Ｄ（σ：標準偏差値、Ｄ：平均粒子径）が０．２以下である銅ナノ粒子。
（６）上記（５）の銅ナノ粒子を１ないし８０質量％含んでなる導電性組成物。
（７）上記（６）の導電性組成物を用いて形成された被覆層を有する電子デバイス。
According to the studies by the present inventors, it has been found that the above problems can be achieved by the following invention.
(1) In a reactor equipped with a stirrer , a reducing agent is added to a solution containing an organic acid copper salt and a monoamine compound having 8 to 16 carbon atoms , and copper nanoparticles are formed and grown to produce copper nanoparticles. The copper metal nuclei are formed and grown at a temperature of 10 to 55 ° C. and a change in liquid temperature ΔT when a reducing agent is added is 20 ° C. or less. A method for producing copper nanoparticles.
(2) The method for producing copper nanoparticles according to (1), wherein the organic acid copper salt is at least one selected from copper formate, copper acetate, copper oxalate, copper oleate, copper stearate and copper tetradecanoate.
(3) Monoamine compounds having 8 to 16 carbon atoms are octylamine, nonylamine, decylamine, undecylamine, dodecylamine, tridecylamine, tetradecylamine, pentadecylamine, hexadecylamine, dodecyldimethylamine and trioctylamine. The method for producing copper nanoparticles according to (1) or (2), which is at least one selected.
(4) The copper according to any one of the above (1) to (3), wherein the reducing agent is at least one selected from dimethylamine borane, tert-butylamine borane, sodium borohydride, oxalic acid, ascorbic acid, formaldehyde and acetaldehyde. A method for producing nanoparticles.
(5) The average particle diameter (D) prepared by the method for producing copper nanoparticles according to any one of (1) to (4 ) above is 10 nm or less, and σ / D (σ: standard deviation value, D: Copper nanoparticles having an average particle diameter) of 0.2 or less .
(6) A conductive composition comprising 1 to 80% by mass of the copper nanoparticles of (5) above.
(7) An electronic device having a coating layer formed using the conductive composition of (6) above.
本発明の方法によれば、ナノサイズの銅微粒子、具体的には、例えば、平均粒子径が１０ｎｍ以下であり、かつσ／Ｄが０．２の微細で、均一性に優れた銅ナノ粒子を容易に製造することができる。 According to the method of the present invention, nano-sized fine copper particles, specifically, for example, an average particle diameter of at 10nm or less, and sigma / D a is 0.2 micro uniformity excellent copper nanoparticles Can be easily manufactured.
本発明の方法によって得られる銅ナノ粒子を含む導電性組成物を、例えば、回路パターン描画用インクとして使用すると均一な被膜が形成されるため、導電性に優れた金属被膜を得ることができる。 When a conductive composition containing copper nanoparticles obtained by the method of the present invention is used as, for example, a circuit pattern drawing ink, a uniform film is formed, and therefore a metal film having excellent conductivity can be obtained.
本発明によれば、有機酸銅塩と炭素数８〜１６のモノアミン化合物とを反応させて銅ナノ粒子を製造する際に、銅金属核の形成およびその成長を１００℃未満の温度で行う。有機酸銅塩と炭素数８〜１６のモノアミン化合物とを反応させて銅微粒子を製造すること自体は公知であり、本発明においても、上記有機酸銅塩およびモノアミン化合物としては、この種の反応に一般に知られている有機酸銅塩およびモノアミン化合物を用いることができる（例えば、特許文献１参照）。 According to the present invention, performs a monoamine compound of the organic acid copper salt and 8-16 carbon atoms is reacted in producing copper nanoparticles in form and growth of less than 100 ° C. temperature of the copper metal nuclei . Itself of a monoamine compound of the organic acid copper salt and 8-16 carbon atoms are reacted to produce the fine copper particles are known, in the present invention, as the organic acid copper salt and monoamine compounds, this type it is possible to use an organic acid copper salt of the reaction is generally known and monoamine compound (e.g., see Patent Document 1).
上記有機酸銅塩の具体例としては、ギ酸、酢酸、プロピオン酸、酪酸、イソ酪酸、ヘキサン酸、ヘプタン酸、オクタン酸、ノナン酸、デカン酸、ウンデカン酸、ドデカン酸、テトラデカン酸、オレイン酸、リノール酸、リノレン酸、ステアリン酸、シュウ酸、酒石酸、フタル酸、メタクリル酸、クエン酸、アクリル酸、安息香酸などのカルボン酸やスルホン酸などと、銅との塩を挙げることができる。なかでも、銅のカルボン酸、具体的には、ギ酸銅、酢酸銅、シュウ酸銅、オレイン酸銅、ステアリン酸銅およびテトラデカン酸銅が好適に用いられる。 Specific examples of the organic acid copper salts, formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, dodecanoic acid, tetradecanoic acid, oleic acid, Examples thereof include a salt of copper with a carboxylic acid such as linoleic acid, linolenic acid, stearic acid, oxalic acid, tartaric acid, phthalic acid, methacrylic acid, citric acid, acrylic acid, and benzoic acid, and sulfonic acid. Among these, copper carboxylic acids, specifically copper formate, copper acetate, copper oxalate, copper oleate, copper stearate and copper tetradecanoate are preferably used.
上記炭素数８〜１６のモノアミン化合物の具体例としては、オクチルアミン、ノニルアミン、デシルアミン、ウンデシルアミン、ドデシルアミン、トリデシルアミン、テトラデシルアミン、ペンタデシルアミン、ヘキサデシルアミン、ドデシルジメチルアミンおよびトリオクチルアミンが挙げられる。これらは１種でも、あるいは２種以上混合して使用してもよい。 Specific examples of the monoamine compounds of the 8 to 16 carbon atoms, octylamine, nonylamine, decylamine, undecylamine, dodecylamine, tridecylamine, tetradecylamine, pentadecylamine amine, hexadecylamine, dodecylamine dimethylamine and Trioctylamine is mentioned . These may be used alone or in combination of two or more.
有機酸銅塩とモノアミン化合物との割合については、特に限定されるものではないが、通常、モノアミン化合物を有機酸銅塩１モルに対し０．５モル以上３０モル未満、好ましくは３モル以上１５モル未満の割合で使用する。０．５モルより少ないと、有機酸銅塩とモノアミン化合物との均一な混合物が調製できないため還元時に凝集が生じやすくなり、一方、３０モル以上添加しても微粒子化には作用せず余分なコストが必要となる。 The ratio of the organic acid copper salt and monoamine compound, is not particularly limited, monoamine compound and the organic acid copper salt 1 mole less than 30 mol 0.5 mol or more, preferably 3 moles More than 15 moles are used. If less than 0.5 mol, it aggregation is likely to occur at the time of reduction for homogeneous mixture with the organic acid copper salt and monoamine compounds can not be prepared, while the surplus does not act on micronized be added 30 moles or more Cost is required.
本発明の方法の特徴は、上記の有機酸銅塩とモノアミン化合物との反応を銅金属核の形成およびその成長を１００℃未満の温度で行う点にある。前記特許文献１においては、４０〜８０℃で４〜９６時間行う前段反応と、前段反応より２０〜５０℃高い温度で１０分〜８時間行う後段反応とからなる二段階反応を経て金属微粒子を製造するに対して、本発明においては１０〜５５℃の温度範囲で、液温変化ΔＴ（温度変化範囲）が２０℃以下、好ましくは１０℃以下、より好ましくは５℃以下、特に好ましくは実質的に一定の温度に維持しながら、必要時間、具体的には、例えば、０．１〜５時間、好ましくは０．２〜３時間反応を行うことにより、金属核の形成とその成長を終了させる。このようにすることにより、平均粒子径が１０ｎｍ以下であり、かつσ／Ｄが０．２以下である銅ナノ粒子を効率よく製造することができる。
なお、本発明の「銅金属核の形成およびその成長」とは、銅ナノ粒子の核が形成され、それが成長して目的とする銅ナノ粒子が得られるまでの過程を意味する。
Feature of the process of the present invention is that carried out by forming and growing of less than 100 ° C. the temperature of the reaction of copper metal nuclei and the organic acid copper salt and monoamine compounds. In Patent Document 1, metal fine particles are obtained through a two-stage reaction consisting of a pre-stage reaction performed at 40 to 80 ° C. for 4 to 96 hours and a post-stage reaction performed at a temperature 20 to 50 ° C. higher than the pre-stage reaction for 10 minutes to 8 hours. In contrast to the production, in the present invention, the liquid temperature change ΔT (temperature change range) is 20 ° C. or less, preferably 10 ° C. or less, more preferably 5 ° C. or less, particularly preferably substantially in the temperature range of 10 to 55 ° C. The formation of the metal nucleus and its growth are completed by carrying out the reaction for a required time, specifically, for example, 0.1 to 5 hours, preferably 0.2 to 3 hours, while maintaining the temperature constant. Let By doing in this way, the copper nanoparticle whose average particle diameter is 10 nm or less and (sigma) / D is 0.2 or less can be manufactured efficiently.
The “formation and growth of copper metal nuclei” of the present invention means a process from the formation of nuclei of copper nanoparticles to the growth of the desired copper nanoparticles.
本発明の方法においては、上記の有機酸銅塩とモノアミン化合物との混合物と還元剤との反応の際に、液温変化ΔＴを２０℃以下、好ましくは１０℃以下、より好ましくは５℃以下、特に好ましくは実質的に一定の温度に調整しながら、還元剤を添加して、銅金属核およびその成長を完了させるのがよい。上記還元剤としては、ジメチルアミンボラン、ｔｅｒｔ−ブチルアミンボラン、水素化ホウ素ナトリウム、シュウ酸、アスコルビン酸、ホルムアルデヒドおよびアセトアルデヒドを挙げることができる。これらは２種以上混合して使用することもできる。なかでも、ジメチルアミンボランおよび水素化ホウ素ナトリウムが好適に用いられる。 In the method of the present invention, upon reaction with a mixture with a reducing agent and the organic acid copper salt and monoamine compound, the liquid temperature change [Delta] T 20 ° C. or less, preferably 10 ° C. or less, more preferably 5 ° C. Hereinafter, the copper metal nucleus and its growth are preferably completed by adding a reducing agent while adjusting the temperature to a substantially constant temperature. Examples of the reducing agent include dimethylamine borane, tert-butylamine borane, sodium borohydride, oxalic acid, ascorbic acid, formaldehyde, and acetaldehyde. These may be used in combination of two or more. Of these, dimethylamine borane and sodium borohydride are preferably used.
本発明の方法によれば、平均粒子径（Ｄ）が１０ｎｍ以下、好ましくは２〜８ｎｍ、より好ましくは３〜７ｎｍであり、かつσ／Ｄ（σ：標準偏差値、Ｄ：平均粒子径）が０．２以下、好ましくは０．０１〜０．１９、より好ましくは０．０２〜０．１８である銅ナノ粒子が得られる。本発明においては、電界放射型走査電子顕微鏡（ＦＥ−ＳＥＭ）を使用して金属ナノ粒子の粒子径を測定し、その平均値および標準偏差値を算出した。なお、本発明の「銅ナノ粒子」とは、銅ナノ粒子のほかに、銅酸化物ナノ粒子、あるいは銅ナノ粒子と銅酸化物ナノ粒子との混合物を包含するものである。例えば、銅はＣｕ２ Ｏ、ＣｕＯなどの酸化物の形態で存在する。 According to the method of the present invention, the average particle size (D) is 10 nm or less, preferably 2 to 8 nm, more preferably 3 to 7 nm, and σ / D (σ: standard deviation value, D: average particle size). but 0.2 or less, preferably 0.01 to 0.19, copper nanoparticles are obtained and more preferably from 0.02 to 0.18. In the present invention, the particle diameter of the metal nanoparticles was measured using a field emission scanning electron microscope (FE-SEM), and the average value and the standard deviation value were calculated. Note that the "copper nanoparticles" of the present invention, in addition to the copper nanoparticles, is intended to encompass a mixture of copper oxide nanoparticles or copper nanoparticles, and copper oxide nanoparticles. For example, copper exists in the form of oxides such as Cu 2 O and CuO.
上記還元剤は、有機酸銅塩１モルに対し、０．１モル以上１０モル未満、好ましくは０．３モル以上５モル未満の割合で用いるのが一般的である。１０モル以上では、還元力が強すぎるため粒子が凝集し銅ナノ粒子が得られなくなり、一方、０．１モルより少ないと十分に還元できないため銅ナノ粒子が生成しない。 The reducing agent is, relative to the organic acid copper salt 1 mole, less than 10 mol 0.1 mol or more, preferably common to use a ratio of less than 5 mol 0.3 mol. If the amount is 10 mol or more, the reducing power is too strong and the particles aggregate and copper nanoparticles cannot be obtained. On the other hand, if the amount is less than 0.1 mol, the particles cannot be sufficiently reduced and copper nanoparticles are not generated.
上記還元剤の添加方法には特に制限はなく、還元剤を水に溶解して水溶液として添加するのが一般的である。具体的には、有機酸銅塩とモノアミン化合物との混合物に、反応液を１００℃未満とし、さらに液温変化ΔＴを２０℃以下に調整しながら、還元剤を所定時間内に徐々に添加すればよい。 There is no restriction | limiting in particular in the addition method of the said reducing agent, It is common to dissolve a reducing agent in water and to add as aqueous solution. More specifically, the mixture of an organic acid copper salt and monoamine compound, the reaction solution is less than 100 ° C., while further adjusting the liquid temperature change ΔT in 20 ° C. or less, gradually adding a reducing agent within a predetermined time do it.
上記の有機酸銅塩とモノアミン化合物と還元剤との反応によって得られる銅ナノ粒子は、未反応のモノアミン化合物や還元剤から生成する生成物などとともに反応液中に含まれているため、アセトン、エタノール、メタノール、水など加えて静置した後、メンブレンフィルターなどを用いてろ過することにより、銅ナノ粒子をモノアミン化合物とともに沈殿物として回収することができる。 Since the above-mentioned copper nanoparticles obtained by the reaction of an organic acid copper salt and monoamine compound and a reducing agent are included with such products formed from monoamine compound or a reducing agent of the unreacted in the reaction solution, acetone, ethanol, allowed to stand added methanol, water, etc., by filtration using a membrane filter, it is possible to recover the copper nano-particles as a precipitate with monoamine compound.
次に、上記銅ナノ粒子の沈殿物を再度溶媒に分散させる。この溶媒としては、ノルマルヘキサン、シクロヘキサン、ノルマルペンタン、ノルマルヘプタン、トルエン、キシレン、メチルイソブチルケトン、ベンゼン、クロロホルム、四塩化炭素、メチルエチルケトン、酢酸エチル、酢酸ブチル、酢酸イソブチル、エチルベンゼン、トリメチルベンゼン、テルピネオール、デカン、ウンデカン、ドデカン、テトラデカン、ヘキサデカン、メタノール、エタノール、プロピルアルコール、ブチルアルコールなどを用いることができる。溶媒量は、沈殿物に対して質量で１倍以上１００倍未満、好ましくは３倍以上５０倍未満である。１００倍以上使用しても溶解性に変化はなく、１倍未満では金属ナノ粒子の分散体を調製することができない。 Next, the precipitate of the copper nanoparticles is dispersed again in the solvent. As this solvent, normal hexane, cyclohexane, normal pentane, normal heptane, toluene, xylene, methyl isobutyl ketone, benzene, chloroform, carbon tetrachloride, methyl ethyl ketone, ethyl acetate, butyl acetate, isobutyl acetate, ethylbenzene, trimethylbenzene, terpineol, Decane, undecane, dodecane, tetradecane, hexadecane, methanol, ethanol, propyl alcohol, butyl alcohol, and the like can be used. The amount of the solvent is 1 to 100 times, preferably 3 to 50 times by mass with respect to the precipitate. Even if it is used 100 times or more, the solubility does not change, and if it is less than 1 time, a dispersion of metal nanoparticles cannot be prepared.
上記溶媒に沈殿物を分散させたものを銅ナノ粒子分散液として使用してもよいが、分散液に含まれる不純物を取り除くとの観点から、分散液を５℃以下にまで冷却した後、再度メンブレンフィルターなどでろ過を行い、そのろ過液を銅ナノ粒子分散液として使用することが好ましい。また、更に好ましくは、上記ろ過液中の溶媒を減圧除去させた後、再度上記溶媒に分散させることにより、不純物が少なく、かつ銅ナノ粒子を高濃度に含有した銅ナノ粒子分散液を調製することができる。 A dispersion in which a precipitate is dispersed in the above-mentioned solvent may be used as a copper nanoparticle dispersion. However, from the viewpoint of removing impurities contained in the dispersion, the dispersion is cooled to 5 ° C. or lower and then again. It is preferable to perform filtration with a membrane filter or the like and use the filtrate as a copper nanoparticle dispersion. Further, more preferably, after the solvent of the filtrate in is removed under reduced pressure, by dispersing again the solvent, impurities less, and preparing a copper nanoparticle dispersion containing the copper nano-particles in a high concentration be able to.
本発明の導電性組成物とは、平均粒子径が１０ｎｍ以下であり、かつσ／Ｄが０．２以下である銅ナノ粒子を１〜８０質量％、好ましくは３０〜６０質量％含有するものであり、通常、前記銅ナノ粒子の有機溶剤分散液について、その銅ナノ粒子の含有量を１〜８０質量％とすることにより容易に得られる。この導電性組成物は、電子デバイスにおける導電性パターンを作成するための、導電パターン描画用インク組成物として好適に用いられる。 The conductive composition of the present invention contains 1 to 80% by mass, preferably 30 to 60% by mass of copper nanoparticles having an average particle size of 10 nm or less and σ / D of 0.2 or less. , and the usually, an organic solvent dispersion of the copper nanoparticles, can be easily obtained by controlling the content of the copper nanoparticles and 1 to 80 wt%. This conductive composition is suitably used as a conductive pattern drawing ink composition for creating a conductive pattern in an electronic device.
本発明の導電性組成物を所定の基板に塗布した後、熱処理することにより銅ナノ粒子からなる被覆層が形成される。導電性組成物を基板に塗布する方法については特に制限はなく、この種の分散体の塗布に一般に用いられている方法にしたがって行うことができる。具体的には、例えば、スクリーン印刷法、ディップコーティング法、スプレー法、スピンコーティング法などを採用することができる。上記基板としては、電極、配線、回路などを構成するのに一般に用いられている、焼成によって焼失、劣化しない耐熱性のものであればいずれでもよい。具体的には、例えば、鉄、銅、アルミニウムなどの金属基板、ポリイミドフィルムなどの耐熱性樹脂基板、ガラス基板などを挙げることができる。また、上記熱処理は、真空中、不活性ガス中、酸化性ガス、還元性ガス中のいずれかの雰囲気において実施することが好ましく、また、その際の熱処理温度は５０℃以上５００℃未満であることが好ましい。この被覆層は当該銅金属成分から構成されるものであり、銅金属それ自体に相当する導電性を示す。銅は、比抵抗値が低いこと、また耐エレクトロマイグレーション性の観点から好適である。 After apply | coating the electrically conductive composition of this invention to a predetermined board | substrate, the coating layer which consists of copper nanoparticles is formed by heat-processing. There is no restriction | limiting in particular about the method of apply | coating an electroconductive composition to a board | substrate, It can carry out according to the method generally used for application | coating of this kind of dispersion. Specifically, for example, a screen printing method, a dip coating method, a spray method, a spin coating method, or the like can be employed. As the substrate, any substrate may be used as long as it has a heat resistance generally used for constituting electrodes, wirings, circuits, etc. and does not burn and deteriorate due to firing. Specific examples include metal substrates such as iron, copper, and aluminum, heat resistant resin substrates such as polyimide films, and glass substrates. Further, the heat treatment is preferably performed in an atmosphere of any one of vacuum, inert gas, oxidizing gas, and reducing gas, and the heat treatment temperature at that time is 50 ° C. or higher and lower than 500 ° C. It is preferable. This coating layer is comprised from the said copper metal component, and shows the electroconductivity equivalent to copper metal itself. Copper, specific resistance value is low, also suitable in view of electromigration resistance.
また、本発明の電子デバイスとは、上記導電性組成物を所望の形状に形成した被覆層、具体的には、例えば、金属配線および端子電極を有するものであり、その具体例としては、積層チップキャパシタ、積層チップインダクタ、チップ抵抗器、ビルドアップ基板、フレキシブルプリント基板、ガラス基板、セラミック基板などを挙げることができる。 Further, the electronic device of the present invention has a coating layer formed by forming the conductive composition into a desired shape, specifically, for example, a metal wiring and a terminal electrode. A chip capacitor, a multilayer chip inductor, a chip resistor, a build-up substrate, a flexible printed substrate, a glass substrate, a ceramic substrate, and the like can be given.
本発明の有利な実施態様を示している以下の実施例を挙げて、本発明を更に具体的に説明する。
（実施例１）
１Ｌのガラスビーカーに酢酸銅一水和物（和光純薬工業株式会社製）１５．７ｇとオクチルアミン（和光純薬工業株式会社）１０１．６ｇとを仕込み、４０℃で１０分間攪拌混合した。次に、前記ガラスビーカーを３０℃の恒温水槽に入れ、これに、溶解させたジメチルアミンボラン溶液を液温が４０℃付近となるようにし、０．５時間かけて徐々に添加して、還元処理を行い、金属核の形成およびその成長を終了させた。
The invention is further illustrated by the following examples, which illustrate advantageous embodiments of the invention.
Example 1
A 1 L glass beaker was charged with 15.7 g of copper acetate monohydrate (manufactured by Wako Pure Chemical Industries, Ltd.) and 101.6 g of octylamine (Wako Pure Chemical Industries, Ltd.), and stirred and mixed at 40 ° C. for 10 minutes. Next, the glass beaker is placed in a constant temperature water bath at 30 ° C., and the dissolved dimethylamine borane solution is adjusted so that the liquid temperature becomes around 40 ° C. Processing was performed to finish the formation of metal nuclei and their growth.
上記還元処理後の溶液にアセトン２００ｇを添加し、しばらく放置した後、ろ過により銅および有機物からなる沈殿物を０．１μｍの孔径を有するメンブレンフィルターで分離回収した。回収物にトルエンを添加し再溶解した後、１０℃まで冷却した後、再度メンブレンフィルターでろ過した。続いて、トルエンを減圧除去した後、テトラデカン溶媒を添加し、銅ナノ粒子を４０質量％含有する分散液が得られた。 200 g of acetone was added to the solution after the reduction treatment and left for a while, and then a precipitate made of copper and an organic substance was separated and collected by filtration with a membrane filter having a pore size of 0.1 μm. Toluene was added to the recovered material and redissolved, and then cooled to 10 ° C., and then filtered again with a membrane filter. Subsequently, after toluene was removed under reduced pressure, a tetradecane solvent was added to obtain a dispersion containing 40% by mass of copper nanoparticles.
上記分散液をＦＥ−ＳＥＭにより観察したところ、銅ナノ粒子の平均粒子径は５ｎｍであり、σ／Ｄの値は０．１４であった。
（比較例１）
１Ｌのガラスビーカーに酢酸銅一水和物（和光純薬工業株式会社製）１５．７ｇとオクチルアミン（和光純薬工業株式会社）１０１．６ｇとを仕込み、４０℃で１０分間攪拌混合した。次に、この混合溶液を１２０℃まで昇温した後、溶解させたジメチルアミンボラン溶液を添加し還元処理を実施した。還元時の温度は１２０℃でほぼ安定していた。
When the dispersion was observed by FE-SEM, the average particle diameter of the copper nanoparticles was 5 nm, and the value of σ / D was 0.14.
(Comparative Example 1)
A 1 L glass beaker was charged with 15.7 g of copper acetate monohydrate (manufactured by Wako Pure Chemical Industries, Ltd.) and 101.6 g of octylamine (Wako Pure Chemical Industries, Ltd.), and stirred and mixed at 40 ° C. for 10 minutes. Next, after raising the temperature of this mixed solution to 120 ° C., a dissolved dimethylamine borane solution was added to perform a reduction treatment. The temperature during the reduction was almost stable at 120 ° C.
還元後の溶液を４０℃まで冷却した後、実施例１と同様の方法で銅ナノ粒子を４０質量％含有する分散液の調製を試みた。実施例１では、０．１μｍの孔径を有するメンブレンフィルターのろ過は容易であったが、本調製ではろ過が非常に困難であり、１μｍの孔径を有するメンブレンフィルターでろ過を実施したが、１０倍の時間を要した。 After the reduced solution was cooled to 40 ° C., an attempt was made to prepare a dispersion containing 40% by mass of copper nanoparticles in the same manner as in Example 1. In Example 1, filtration of a membrane filter having a pore size of 0.1 μm was easy, but in this preparation, filtration was very difficult, and filtration was performed with a membrane filter having a pore size of 1 μm. It took time.
また、分散液をＦＥ−ＳＥＭにより観察したところ、銅ナノ粒子の平均粒子径は２０ｎｍであり、σ／Ｄの値は０．４０であることが確認された。 Moreover, when the dispersion liquid was observed by FE-SEM, it was confirmed that the average particle diameter of the copper nanoparticles was 20 nm and the value of σ / D was 0.40.
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