WO2012133296A1 - Composite of organic compound and silver core/copper shell nanoparticles and method for producing same - Google Patents
Composite of organic compound and silver core/copper shell nanoparticles and method for producing same Download PDFInfo
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- WO2012133296A1 WO2012133296A1 PCT/JP2012/057738 JP2012057738W WO2012133296A1 WO 2012133296 A1 WO2012133296 A1 WO 2012133296A1 JP 2012057738 W JP2012057738 W JP 2012057738W WO 2012133296 A1 WO2012133296 A1 WO 2012133296A1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
Definitions
- the object of the present invention is to form a silver core copper shell nanoparticle having a small particle size with a uniform particle size, which can be stably dispersed in a medium, exhibit oxidation resistance, and form a film. It is to provide a complex with an organic compound useful as a protective agent capable of exhibiting high conductivity when post-baking, and to provide a simple production method thereof.
- the present inventors have used an organic compound having an appropriate coordination power such as the above-mentioned thioether (CSC) as a protective agent. I thought it was desirable to choose. Moreover, it was considered important to develop a melting point drop (so-called Kubo effect) due to the nanosize effect by controlling the particle size to be small and uniform. However, when the diameter is remarkably reduced, the specific surface area is increased and the oxidation resistance is lowered. Therefore, it was considered that metal nanoparticles containing copper having a particle diameter of about 20 to 50 nm are suitable from the balance of both.
- CSC thioether
- the polymer selected as the protective agent by the present inventor specifically has a structure represented by the following general formula (1).
- An average particle diameter (primary particle diameter) of 100 particles of the composite according to the TEM image is preferably in the range of 1 to 100 nm when used as a conductive material or the like.
- the average particle size obtained by the dynamic light scattering method is larger than the particle size obtained by TEM observation and is about 5 to 110 nm.
- a solvent that is suitable for the purpose of use is added and the medium is exchanged to obtain a dispersion in which the composite is dispersed in the medium selected according to the purpose. Can be prepared.
- this reaction mixture was circulated through a hollow fiber type ultrafiltration membrane module (HIT-1-FUS1582, 145 cm 2, molecular weight cut off 150,000) manufactured by Daisen Membrane Systems Co., Ltd. and subjected to nitrogen bubbling.
- A% hydrazine aqueous solution was circulated until the filtrate from the ultrafiltration module reached about 500 mL while being added in the same amount as the leaching filtrate.
- the supply of the 0.1% hydrazine aqueous solution was stopped and concentrated to obtain 27.9 g of a silver core copper shell nanoparticle dispersion.
- the non-volatile content in the dispersion was 15%, and the metal content in the non-volatile was 95%.
- Example 13 The nucleating agent usage ratio was changed to 7.0 milligram atoms of silver nanoparticles.
- the usage ratio of the silver nanoparticle dispersion 1 of Example 1 (particle size 25 nm, silver 3.0 milligram atoms, water solvent) was changed to silver.
- a silver core copper shell nanoparticle dispersion was prepared in the same manner as in Example 1 except that the concentration was 7.0 milligram atoms.
Abstract
Description
X-(OCH2CHR1)n-O-CH2-CH(OH)-CH2-S-Z (1)
〔式(1)中、XはC1~C8のアルキル基であり、R1は水素原子又はメチル基であり、nは2~100の繰り返し数を示す整数であって、R1は繰り返し単位ごとに独立し、同一であっても異なっていても良く、ZはC2~C12のアルキル基、アリル基、アリール基、アリールアルキル基、-R2-OH、-R2-NHR3、又は-R2-(COR4)m(但し、R2はC1~C4の飽和炭化水素基であり、R3は水素原子、C2~C4のアシル基、C2~C4のアルコキシカルボニル基、又は芳香環上にC1~C4のアルキル基又はC1~C8のアルコキシ基を置換基として有していても良いベンジルオキシカルボニル基であり、R4はヒドロキシ基、C1~C4のアルキル基又はC1~C8のアルコキシ基であり、mは1~3である。)で表される基である。〕で表されるチオエーテル含有有機化合物(A)と、銀コア銅シェルナノ粒子(B)との複合体を提供するものである。 That is, the present invention provides the following general formula (1)
X— (OCH 2 CHR 1 ) n —O—CH 2 —CH (OH) —CH 2 —SZ (1)
[In the formula (1), X is a C 1 to C 8 alkyl group, R 1 is a hydrogen atom or a methyl group, n is an integer indicating a repeating number of 2 to 100, and R 1 is a repeating group. Each unit is independent and may be the same or different. Z is a C 2 to C 12 alkyl group, allyl group, aryl group, arylalkyl group, —R 2 —OH, —R 2 —NHR 3 Or —R 2 — (COR 4 ) m (where R 2 is a C 1 -C 4 saturated hydrocarbon group, R 3 is a hydrogen atom, a C 2 -C 4 acyl group, C 2 -C 4) Or a benzyloxycarbonyl group optionally having a C 1 -C 4 alkyl group or a C 1 -C 8 alkoxy group as a substituent on the aromatic ring, R 4 is a hydroxy group, Al of C 1 ~ C 4 alkyl or C 1 ~ C 8 An alkoxy group, m is a group represented by 1-3.). ] The composite of the thioether containing organic compound (A) represented by this, and a silver core copper shell nanoparticle (B) is provided.
前述のとおり、導電性材料として有用な銀コア銅シェルナノ粒子を分散させる場合の保護剤には、分散安定性、耐酸化性及び低温焼結性が要求される。分散安定性を発現するためには、保護剤の金属親和性部位の配位が保存中に外れない必要がある。また耐酸化性についても、保護剤の配位性が強い方が金属ナノ粒子の表面を有機化合物が覆うために、酸素の接触を妨げることが可能となる。しかし一方、低温焼結性のためには焼結時に金属親和性部位の配位が外れた方が金属ナノ粒子の融着が進行しやすい。これら相反する配位の強さを満たすためには、強すぎず弱すぎない適度な配位力が必要となる。そのような金属親和性部位として、チオエーテル基が適していることを見出した。 [Thioether-containing organic compound (A)]
As described above, the dispersion agent, the oxidation resistance, and the low temperature sintering property are required for the protective agent in the case of dispersing silver core copper shell nanoparticles useful as a conductive material. In order to exhibit dispersion stability, it is necessary that the coordination of the metal affinity site of the protective agent is not removed during storage. As for the oxidation resistance, when the protective agent has a higher coordination property, the surface of the metal nanoparticles is covered with the organic compound, so that contact with oxygen can be prevented. On the other hand, for low-temperature sinterability, the fusion of the metal nanoparticles is more likely to proceed if the metal affinity site is out of coordination during sintering. In order to satisfy these conflicting coordination strengths, an appropriate coordination force that is neither too strong nor too weak is required. It has been found that a thioether group is suitable as such a metal affinity site.
〔式(1)中、XはC1~C8のアルキル基であり、R1は水素原子又はメチル基であり、nは2~100の繰り返し数を示す整数であって、R1は繰り返し単位ごとに独立し、同一であっても異なっていても良く、ZはC2~C12のアルキル基、アリル基、アリール基、アリールアルキル基、-R2-OH、-R2-NHR3、又は-R2-(COR4)m(但し、R2はC1~C4の飽和炭化水素基であり、R3は水素原子、C2~C4のアシル基、C2~C4のアルコキシカルボニル基、又は芳香環上にC1~C4のアルキル基又はC1~C8のアルコキシ基を置換基として有していても良いベンジルオキシカルボニル基であり、R4はヒドロキシ基、C1~C4のアルキル基又はC1~C8のアルコキシ基であり、mは1~3である。)で表される基である。〕 X— (OCH 2 CHR 1 ) n —O—CH 2 —CH (OH) —CH 2 —SZ (1)
[In the formula (1), X is a C 1 to C 8 alkyl group, R 1 is a hydrogen atom or a methyl group, n is an integer indicating a repeating number of 2 to 100, and R 1 is a repeating group. Each unit is independent and may be the same or different. Z is a C 2 to C 12 alkyl group, allyl group, aryl group, arylalkyl group, —R 2 —OH, —R 2 —NHR 3 Or —R 2 — (COR 4 ) m (where R 2 is a C 1 -C 4 saturated hydrocarbon group, R 3 is a hydrogen atom, a C 2 -C 4 acyl group, C 2 -C 4) Or a benzyloxycarbonyl group optionally having a C 1 -C 4 alkyl group or a C 1 -C 8 alkoxy group as a substituent on the aromatic ring, R 4 is a hydroxy group, Al of C 1 ~ C 4 alkyl or C 1 ~ C 8 An alkoxy group, m is a group represented by 1-3.). ]
前述のように、本発明において用いる保護剤は、前記一般式(1)で表される化合物である。この有機化合物(A)を合成する方法について、以下詳述する。 [Method for producing thioether-containing organic compound (A)]
As described above, the protective agent used in the present invention is a compound represented by the general formula (1). The method for synthesizing this organic compound (A) will be described in detail below.
本発明の有機化合物(A)と銀コア銅シェルナノ粒子(B)との複合体は、銀コア銅シェルナノ粒子がチオエーテル含有有機化合物(A)によって被覆され、全体として粒子状の複合体となっているものである。当該複合体の粒子径は、大きすぎると製膜性や分散安定性が悪くなり、小さすぎると表面積が増えるため酸化し易くなるため、1~100nmの平均粒子径を有することが好ましく、20~50nmの平均粒子径を有することがさらに好ましい。 [Composite of Organic Compound (A) and Silver Core Copper Shell Nanoparticle (B)]
The composite of the organic compound (A) of the present invention and the silver core copper shell nanoparticle (B) has a silver core copper shell nanoparticle coated with the thioether-containing organic compound (A) to form a particulate composite as a whole. It is what. When the particle size of the composite is too large, the film-forming property and dispersion stability are deteriorated. When the particle size is too small, the surface area is increased and the film is easily oxidized. Therefore, the composite preferably has an average particle size of 1 to 100 nm. More preferably, it has an average particle size of 50 nm.
本発明の有機化合物(A)と銀コア銅シェルナノ粒子(B)との複合体は、前述のチオエーテル含有有機化合物(A)と溶媒、銀ナノ粒子、酸化銅(I)及び/又は酸化銅(II)、を混合する工程(i)と、酸化銅を還元することで銀ナノ粒子の周りに銅のシェルを生成させる工程(ii)と、を有することを特徴とするものである。 [Method for producing composite of organic compound (A) and silver core copper shell nanoparticles (B)]
The composite of the organic compound (A) of the present invention and the silver core copper shell nanoparticle (B) comprises the aforementioned thioether-containing organic compound (A) and solvent, silver nanoparticle, copper oxide (I) and / or copper oxide ( II), and a step (ii) of forming copper shells around the silver nanoparticles by reducing copper oxide.
得られた複合体の分散体を、バーコーター等で基材に塗布し、不活性ガス中で乾燥させると、それだけで金属光沢を有する薄膜が得られる。空気中で乾燥させても同様に金属光沢膜となる。これを、窒素雰囲気下で250℃、3時間加熱した後、比抵抗と膜厚を測定して薄膜の導電性を評価することにより、導電性材料としての機能が評価できる。 [Conductivity of thin film]
When the obtained composite dispersion is applied to a substrate with a bar coater or the like and dried in an inert gas, a thin film having a metallic luster can be obtained by itself. Even if it is dried in the air, a metallic gloss film is obtained. After heating this at 250 ° C. for 3 hours in a nitrogen atmosphere, the function as a conductive material can be evaluated by measuring the specific resistance and film thickness and evaluating the conductivity of the thin film.
0.03%テトラメチルシラン含有重クロロホルム約0.8mLに、測定する化合物約20mgを溶かし、これを外径5mmのガラス製NMR測定用サンプル管に入れ、JEOL JNM-LA300型核磁気共鳴吸収スペクトル測定装置により1H-NMRスペクトルを取得した。化学シフト値δは、テトラメチルシランを基準物質として表わした。 Measurement of 1 H-NMR About 20 mg of a compound to be measured was dissolved in about 0.8 mL of 0.03% tetramethylsilane-containing deuterated chloroform, and this was put into a glass-made NMR measurement sample tube with an outer diameter of 5 mm, and JEOL JNM-LA300 A 1 H-NMR spectrum was obtained by a type nuclear magnetic resonance absorption spectrum measuring apparatus. The chemical shift value δ was expressed using tetramethylsilane as a reference substance.
エチレングリコール約10mLに、複合体の分散体少量を加えて振り混ぜ、直ちに日本分光工業社製MV-2000型フォトダイオードアレイ式紫外可視吸収スペクトル測定装置を用いて、400nm~800nmまで0.1秒間で掃引して、紫外可視吸収スペクトルを測定した。 Measurement of UV-visible absorption spectrum Add a small amount of the complex dispersion to about 10 mL of ethylene glycol and shake it. Immediately use an MV-2000 type photodiode array type UV-visible absorption spectrum measuring device manufactured by JASCO Corporation. The ultraviolet-visible absorption spectrum was measured by sweeping to 800 nm in 0.1 second.
得られた金属薄膜について、表面抵抗率(Ω/□)をロレスタ-GP MCP-T610型低抵抗率計(三菱化学株式会社製)を用い、JIS K7194「導電性プラスチックの4探針法による抵抗率試験」に準拠して測定した。薄膜厚み(cm)と表面抵抗率(Ω/□)から体積抵抗率(Ωcm)を次式により算出した。
体積抵抗率(Ωcm)=表面抵抗率(Ω/□)×厚み(cm)
なお、金属薄膜の厚みは、1LM15型走査型レーザー顕微鏡(レーザーテック株式会社製)を用いて計測した。 Measurement of electrical resistivity of metal thin film The obtained metal thin film was measured for surface resistivity (Ω / □) using a Loresta-GP MCP-T610 type low resistivity meter (Mitsubishi Chemical Corporation). It was measured in accordance with “Resistivity test by plastic 4-probe method”. The volume resistivity (Ωcm) was calculated from the following equation from the thin film thickness (cm) and the surface resistivity (Ω / □).
Volume resistivity (Ωcm) = Surface resistivity (Ω / □) × Thickness (cm)
The thickness of the metal thin film was measured using a 1LM15 scanning laser microscope (manufactured by Lasertec Corporation).
TEM観察
不活性雰囲気下で、少量の分散体をエタノールで希釈し、その一滴を電子顕微鏡観察用コロジオン膜付銅グリッドに滴下し、乾燥した後、これをJEM-2200FS型透過型電子顕微鏡(200kv、日本電子株式会社製)を用いて検鏡観察し、得られた写真像から粒子径を計測した。 Measurement of particle size and particle size distribution TEM observation A small amount of dispersion was diluted with ethanol in an inert atmosphere, one drop was dropped onto a copper grid with a collodion film for electron microscope observation, dried, and then JEM- Microscopic observation was performed using a 2200FS transmission electron microscope (200 kv, manufactured by JEOL Ltd.), and the particle diameter was measured from the obtained photographic image.
分散体の一部をエチレングリコールで希釈し、FPAR-1000型濃厚系粒径アナライザー(大塚電子株式会社製)により、粒子径分布、平均粒子径を測定した。このとき、測定を25℃で行い、媒体の屈折率を1.4306、粘度を17.4cPとして解析した。 Particle size distribution measurement by dynamic light scattering method A part of the dispersion was diluted with ethylene glycol, and the particle size distribution and average particle size were measured with an FPAR-1000 type concentrated particle size analyzer (Otsuka Electronics Co., Ltd.). . At this time, the measurement was performed at 25 ° C., and the medium was analyzed with a refractive index of 1.4306 and a viscosity of 17.4 cP.
金属薄膜:金属薄膜付きスライドガラスを適当な大きさに切断して試料台に載せ、直ちにRINT TTR2(50kv、300mA、株式会社リガク製)を用いて回折角(2θ)に対する回折X線の強度を測定、記録した。 Wide-angle X-ray diffraction method Metal thin film: A glass slide with a metal thin film is cut to an appropriate size and placed on a sample stage, and immediately diffracted to a diffraction angle (2θ) using RINT TTR2 (50 kv, 300 mA, manufactured by Rigaku Corporation). X-ray intensity was measured and recorded.
得られた分散体約1mLをガラスサンプル瓶にとり、温水上で窒素気流下加熱濃縮し、残渣を更に40℃、8時間真空乾燥して乾固物を得た。この乾固物およそ5mgを熱重量分析用アルミパンに精密にはかり、EXSTAR TG/DTA6300型示差熱重量分析装置(セイコーインスツル株式会社製)に載せ、窒素気流下、室温から500℃まで毎分10℃の割合で昇温して、加熱に伴う重量減少率を測定した。金属の含有率は以下の式で算出した。
含有率(%)=100-重量減少率(%) Metal content by thermal analysis (thermogravimetric analysis (TG / DTA method)) About 1 mL of the resulting dispersion is placed in a glass sample bottle, heated and concentrated under hot air in a nitrogen stream, and the residue is further vacuum dried at 40 ° C. for 8 hours. About 5 mg of this dried product was precisely weighed on an aluminum pan for thermogravimetric analysis and placed on an EXSTAR TG / DTA6300 differential thermogravimetric analyzer (Seiko Instruments Inc.), and a nitrogen stream Then, the temperature was increased from room temperature to 500 ° C. at a rate of 10 ° C. per minute, and the weight reduction rate due to heating was measured.
Content rate (%) = 100-weight reduction rate (%)
メチル-3-(3-(メトキシ(ポリエトキシ)エトキシ)-2-ヒドロキシプロピルスルファニル)プロピオナート
(ポリエチレングリコールメチルグリシジルエーテル(ポリエチレングリコール鎖の分子量2000)への3-メルカプトプロピオン酸メチルの付加化合物) Synthesis Example 2 Thioether-containing organic compound (A-1)
Methyl-3- (3- (methoxy (polyethoxy) ethoxy) -2-hydroxypropylsulfanyl) propionate (addition compound of methyl 3-mercaptopropionate to polyethylene glycol methylglycidyl ether (molecular weight of polyethylene glycol chain 2000))
特開2010-209421号公報の実施例12に記載の方法にて高分子化合物を作製した。イオウ含有残基が2-(メトキシカルボニル)エチルチオ基であり、リン酸官能基を有する高分子化合物の合成を行った。MEK70部を、窒素気流中80℃に保ち、攪拌しながら2-メタクリロイルオキシエチルホスフェート5部、メトキシポリエチレングリコールメタクリレート;分子量100、15部、メトキシポリエチレングリコールメタクリレート;分子量1000、80部およびβ-メルカプトプロピオン酸メチル2部、MEK80部からなる混合物、および重合開始剤「パーブチル(登録商標)O、日油株式会社」0.5部、MEK5部からなる混合物を2時間かけて滴下した。滴下終了後、「パーブチル(登録商標)O」1部を添加し、80℃で12時間攪拌した。得られた樹脂溶液に水を加え、減圧脱溶剤した後、水を加えて不揮発分を調製した。このようにして、末端に2-(メトキシカルボニル)エチルチオ基を有する高分子化合物の水溶液を得た(不揮発分40%)。 (Synthesis Example 3) Synthesis of Dispersant for Silver Nanoparticle Production A polymer compound was produced by the method described in Example 12 of JP2010-209421A. A high molecular compound having a sulfur-containing residue of 2- (methoxycarbonyl) ethylthio group and having a phosphate functional group was synthesized. 70 parts of MEK are kept at 80 ° C. in a nitrogen stream, and 5 parts of 2-methacryloyloxyethyl phosphate, methoxypolyethylene glycol methacrylate;
特開2010-209421号公報の実施例29に記載の方法にて銀ナノ粒子分散液を作製した。上記合成例3で得た末端に2-(メトキシカルボニル)エチルチオ基を有する高分子化合物(固形分に換算して0.261g)を水6mLに溶解し、これに1mol/L硝酸6mLを加えた。硝酸銀1.00g(5.89mmol)を水17.5mLに溶解したものをこれに加え、トリエタノールアミン4.39g(29.43mmol)を加えて60℃で2.5時間攪拌した。得られた懸濁液を限外濾過ユニット(ザルトリウス・ステディム社ビバスピン20、分画分子量10万、2個)で濾過した。濾過残渣に精製水を加えて再び遠心濾過することを4回繰り返し、得られた残渣に水を加えて2.1gの分散液として銀ナノ粒子分散体を得た。固形分約30w/w%、固形分中の銀含量96.2%(TG-DTA)、粒子径25~30nm(TEM)。 (Synthesis Example 4) Preparation of Silver Nanoparticle Dispersion 1 A silver nanoparticle dispersion was prepared by the method described in Example 29 of JP2010-209421A. The polymer compound having a 2- (methoxycarbonyl) ethylthio group at the terminal obtained in Synthesis Example 3 (0.261 g in terms of solid content) was dissolved in 6 mL of water, and 6 mL of 1 mol / L nitric acid was added thereto. . A solution prepared by dissolving 1.00 g (5.89 mmol) of silver nitrate in 17.5 mL of water was added thereto, and 4.39 g (29.43 mmol) of triethanolamine was added thereto, followed by stirring at 60 ° C. for 2.5 hours. The obtained suspension was filtered with an ultrafiltration unit (Sartorius Stedim Vivaspin 20, fractional molecular weight 100,000, 2). Purified water was added to the filtration residue and centrifugal filtration was repeated four times. Water was added to the resulting residue to obtain a silver nanoparticle dispersion as a 2.1 g dispersion. Solid content: about 30 w / w%, silver content in solid content: 96.2% (TG-DTA), particle size: 25-30 nm (TEM).
上記合成例4で得た銀ナノ粒子水分散液1を限外濾過ユニット(ザルトリウス・ステディム社ビバスピン20、分画分子量10万、2個)で濾過した。濾過残渣にエタノールを加えて再び遠心濾過することを4回繰り返し、得られた残渣にエタノールを加えて2.1gの分散液として銀ナノ粒子分散液2(エタノール分散体)を得た。固形分約30w/w%、固形分中の銀含量96.2%(TG-DTA)、粒子径25~30nm(TEM)。 (Synthesis Example 5) Preparation of Silver Nanoparticle Dispersion 2 Silver
特許第4026662号の合成例1に記載の方法にて高分子化合物を作製した。
<ポリエチレングリコール-分岐ポリエチレンイミン-ビスフェノールA型エポキシ樹脂構造を有する高分子化合物の合成>
6-1[トシル化ポリエチレングリコールの合成]
クロロホルム150mlにPEGM〔数平均分子量(Mn)5000〕(アルドリッチ社製)150g〔30mmol〕とピリジン24g(300mmol)とを混合した溶液と、トシルクロライド29g(150mmol)とクロロホルム30mlとを均一に混合した溶液をそれぞれ調製した。PEGMとピリジンの混合溶液を20℃で攪拌しながら、ここにトシルクロライドのトルエン溶液を滴下した。滴下終了後、40℃で2時間反応させた。反応終了後、クロロホルム150ml加えて希釈し、5%HCl水溶液250ml(340mmol)で洗浄後、飽和食塩水と水で洗浄した。得られたクロロホルム溶液を硫酸ナトリウムで乾燥した後、エバポレータで溶媒を留去し、さらに乾燥した。収率は100%であった。1H-NMRスペクトルにより各ピークの帰属を行い(2.4ppm:トシル基中のメチル基、3.3ppm:PEGM末端のメチル基、3.6ppm:PEGのEG鎖、7.3~7.8ppm:トシル基中のベンゼン環)、トシル化ポリエチレングリコールであることを確認した。 (Synthesis Example 6) Synthesis of Dispersant for Preparing Silver Nanoparticles A polymer compound was prepared by the method described in Synthesis Example 1 of Japanese Patent No. 4026662.
<Synthesis of a polymer compound having a polyethylene glycol-branched polyethyleneimine-bisphenol A type epoxy resin structure>
6-1 [Synthesis of tosylated polyethylene glycol]
A solution obtained by mixing 150 g of PEGM [number average molecular weight (Mn) 5000] (manufactured by Aldrich) and 24 g (300 mmol) of pyridine with 150 g of chloroform, and 29 g (150 mmol) of tosyl chloride and 30 ml of chloroform were uniformly mixed. Each solution was prepared. While stirring a mixed solution of PEGM and pyridine at 20 ° C., a toluene solution of tosyl chloride was added dropwise thereto. After completion of the dropping, the reaction was carried out at 40 ° C. for 2 hours. After completion of the reaction, 150 ml of chloroform was added for dilution, washed with 250 ml (340 mmol) of 5% HCl aqueous solution, and then with saturated saline and water. The obtained chloroform solution was dried over sodium sulfate, and then the solvent was distilled off with an evaporator and further dried. The yield was 100%. Each peak was assigned by 1 H-NMR spectrum (2.4 ppm: methyl group in tosyl group, 3.3 ppm: methyl group at the end of PEGM, 3.6 ppm: EG chain of PEG, 7.3 to 7.8 ppm) : Benzene ring in tosyl group) and tosylated polyethylene glycol.
上記1-1で得られたトシル化ポリエチレングリコール23.2g(4.5mmol)と、分岐状ポリエチレンイミン(日本触媒株式会社製、エポミンSP200)15.0g(1.5mmol)をDMA180mlに溶解後、炭酸カリウム0.12gを加え、窒素雰囲気下、100℃で6時間反応させた。反応終了後、固形残渣を除去し、酢酸エチル150mlとヘキサン450mlの混合溶媒を加え、沈殿物を得た。該沈殿物をクロロホルム100mlに溶解し、再度酢酸エチル150mlとヘキサン450mlの混合溶媒を加えて再沈させた。これをろ過し、減圧下で乾燥した。1H-NMRスペクトルにより各ピークの帰属を行い(2.3~2.7ppm:分岐PEIのエチレン、3.3ppm:PEG末端のメチル基、3.6ppm:PEGのEG鎖)、PEG-分岐PEI構造を有する高分子化合物であることを確認した。収率は99%であった。 6-2 [Polyethylene glycol-synthesis of polymer compound having branched polyethyleneimine structure]
After dissolving 23.2 g (4.5 mmol) of the tosylated polyethylene glycol obtained in 1-1 and 15.0 g (1.5 mmol) of branched polyethyleneimine (manufactured by Nippon Shokubai Co., Ltd., Epomin SP200) in 180 ml of DMA, Potassium carbonate 0.12g was added and it was made to react at 100 degreeC under nitrogen atmosphere for 6 hours. After completion of the reaction, the solid residue was removed, and a mixed solvent of 150 ml of ethyl acetate and 450 ml of hexane was added to obtain a precipitate. The precipitate was dissolved in 100 ml of chloroform and reprecipitated again by adding a mixed solvent of 150 ml of ethyl acetate and 450 ml of hexane. This was filtered and dried under reduced pressure. Each peak was assigned by 1 H-NMR spectrum (2.3 to 2.7 ppm: ethylene of branched PEI, 3.3 ppm: methyl group at the PEG end, 3.6 ppm: EG chain of PEG), PEG-branched PEI It was confirmed that the polymer compound had a structure. The yield was 99%.
EPICLON AM-040-P(DIC株式会社製、固形ビスフェノールA型エポキシ樹脂)37.4g(20mmol)、4-フェニルフェノール2.72g(16mmol)をDMA100mlに溶解後、65%酢酸エチルトリフェニルホスホニウムエタノール溶液0.52mlを加え、窒素雰囲気下、120℃で6時間反応させた。放冷後、多量の水中に滴下し、得られた沈殿物をさらに多量の水で洗浄した。再沈精製物をろ過後減圧乾燥し、変性ビスフェノールA型エポキシ樹脂を得た。得られた生成物の収率は100%であった。1H-NMR測定を行いエポキシ基の積分比を考察した結果、ビスフェノールA型エポキシ樹脂1分子にエポキシ環は0.95個残っており、得られた変性エポキシ樹脂は、ビスフェノールA骨格を有する単官能性のエポキシ樹脂であることを確認した。 6-3 [Modification of epoxy resin]
After dissolving 37.4 g (20 mmol) of EPICLON AM-040-P (manufactured by DIC Corporation, solid bisphenol A type epoxy resin) and 2.72 g (16 mmol) of 4-phenylphenol in 100 ml of DMA, 65% ethyltriphenylphosphonium ethanol 0.52 ml of the solution was added and reacted at 120 ° C. for 6 hours under a nitrogen atmosphere. After allowing to cool, the solution was dropped into a large amount of water, and the resulting precipitate was further washed with a large amount of water. The reprecipitation purified product was filtered and dried under reduced pressure to obtain a modified bisphenol A type epoxy resin. The yield of the obtained product was 100%. As a result of 1 H-NMR measurement and considering the integration ratio of epoxy groups, 0.95 epoxy rings remain in one molecule of the bisphenol A type epoxy resin, and the resulting modified epoxy resin has a single molecule having a bisphenol A skeleton. It was confirmed to be a functional epoxy resin.
上記1-3で得られたポリエチレングリコール-分岐ポリエチレンイミン構造を有する高分子化合物20g(0.8mmol)をメタノール150mlに溶解した溶液に、上記1-3で得られたビスフェノールA型の単官能性エポキシ樹脂4.9g(2.4mmol)をアセトン50mlに溶解した溶液を、窒素雰囲気下で滴下後、50℃で2時間攪拌することで反応を行った。反応終了後、減圧下で溶媒を留去し、さらに減圧乾燥することにより、ポリエチレングリコール-分岐状ポリエチレンイミン-ビスフェノールA型エポキシ樹脂構造を有する高分子化合物(保護剤)を得た。収率は100%であった。得られた高分子化合物30mgを水10mlに加えて攪拌し溶解した。その溶液での粒径分布状態を光散乱法により測定したところ、平均粒径110nmの分散体であり、水中で良好にミセルを形成していることを確認した。 6-4 [Synthesis of dispersant]
The bisphenol A-type monofunctional compound obtained in 1-3 above was added to a solution obtained by dissolving 20 g (0.8 mmol) of the polymer compound having a polyethylene glycol-branched polyethyleneimine structure obtained in 1-3 above in 150 ml of methanol. A solution prepared by dissolving 4.9 g (2.4 mmol) of an epoxy resin in 50 ml of acetone was dropped in a nitrogen atmosphere, and the reaction was performed by stirring at 50 ° C. for 2 hours. After completion of the reaction, the solvent was distilled off under reduced pressure and further dried under reduced pressure to obtain a polymer compound (protective agent) having a polyethylene glycol-branched polyethyleneimine-bisphenol A type epoxy resin structure. The yield was 100%. 30 mg of the resulting polymer compound was added to 10 ml of water and dissolved by stirring. When the particle size distribution state in the solution was measured by the light scattering method, it was confirmed that the dispersion had an average particle size of 110 nm and formed micelles well in water.
特許第4026662号の合成例1に記載の方法にて、銀ナノ粒子分散液3を作製した。合成例6で得た保護剤20mg(EIユニット:0.15mmol)を水239gに溶かした溶液1Aと、硝酸銀0.16g(0.97mmol)を水1.30gに溶かした溶液1B、クエン酸ナトリウム0.12g(0.48mmol)を水0.25gに溶かした溶液1Cをそれぞれ調製した。25℃で攪拌しながら、溶液1Aに溶液1Bを加え、続いて溶液1Cを加えた。分散液は次第に焦げ茶色へと変化した。7日間攪拌後、透析により精製し、水分散液を得た。得られた水分散液1部をサンプリングし、10倍希釈液の可視吸収スペクトル測定により400nmにプラズモン吸収スペクトルのピークが認められ、銀ナノ粒子の生成を確認した。TEM写真より、25nm以下の銀ナノ粒子であることを確認した。 (Synthesis example 7) Preparation of silver nanoparticle dispersion liquid 3 By the method of the synthesis example 1 of patent 4026662, the silver nanoparticle dispersion liquid 3 was produced. A solution 1A in which 20 mg (EI unit: 0.15 mmol) of the protective agent obtained in Synthesis Example 6 was dissolved in 239 g of water, a solution 1B in which 0.16 g (0.97 mmol) of silver nitrate was dissolved in 1.30 g of water, sodium citrate Solutions 1C prepared by dissolving 0.12 g (0.48 mmol) in 0.25 g of water were prepared. While stirring at 25 ° C., solution 1B was added to solution 1A, followed by solution 1C. The dispersion gradually changed to dark brown. After stirring for 7 days, it was purified by dialysis to obtain an aqueous dispersion. One part of the obtained aqueous dispersion was sampled, and a peak of a plasmon absorption spectrum was observed at 400 nm by a visible absorption spectrum measurement of a 10-fold diluted solution, confirming the formation of silver nanoparticles. From the TEM photograph, it was confirmed that the silver nanoparticles were 25 nm or less.
メチルエチルケトン(以下、MEK)70部を、窒素気流中80℃に保ち、攪拌しながらメタクリル酸10部、メタクリル酸ベンジル5部、メトキシポリエチレングリコールメタクリレート;分子量1000を85部、チオグリコール酸2部、MEK80部、および重合開始剤(「パーブチル(登録商標)O」〔日油株式会社製〕)4部からなる混合物を2時間かけて滴下した。滴下終了後、「パーブチル(登録商標)O」2部を添加し、80℃で22時間攪拌した。得られた反応混合物に水を加え、減圧脱溶剤した後、水で不揮発分量を調整した(不揮発分41%)。得られた共重合物の重量平均分子量は9800(ゲルパーミエーション・クロマトグラフ法)、酸価は76.5mgKOH/gであった。 (Comparative Synthesis Example 1) Comparative methacrylate copolymer 70 parts of methyl ethyl ketone (hereinafter referred to as MEK) is kept at 80 ° C. in a nitrogen stream and stirred, 10 parts of methacrylic acid, 5 parts of benzyl methacrylate, methoxypolyethylene glycol methacrylate; molecular weight A mixture consisting of 85 parts of 1000, 2 parts of thioglycolic acid, 80 parts of MEK, and 4 parts of a polymerization initiator (“Perbutyl (registered trademark) O” manufactured by NOF Corporation) was added dropwise over 2 hours. After completion of the dropwise addition, 2 parts of “Perbutyl (registered trademark) O” was added and stirred at 80 ° C. for 22 hours. Water was added to the resulting reaction mixture and the solvent was removed under reduced pressure, and the nonvolatile content was adjusted with water (41% nonvolatile content). The obtained copolymer had a weight average molecular weight of 9800 (gel permeation chromatography) and an acid value of 76.5 mgKOH / g.
酸化銅(I)(5.4g、37.5mmol)、上記合成例3で得たチオエーテル含有有機化合物(A-1)(2.254g)、銀ナノ粒子分散液1(粒径25nm、銀3.0ミリグラム原子、水溶媒)、エタノール80mlと水20mlからなる混合物に、窒素を50mL/分の流量で吹き込みながら、40℃まで加熱した。この混合物に、さらにヒドラジン1水和物(7.5g、150mmol)を加えた。40℃に保持したまま2時間攪拌し還元反応を終結させた。 Example 1 Synthesis of Silver Core Copper Shell Nanoparticle Dispersion Using Thioether-Containing Organic Compound (A-1) Copper (I) oxide (5.4 g, 37.5 mmol), containing thioether obtained in Synthesis Example 3 above To a mixture of organic compound (A-1) (2.254 g), silver nanoparticle dispersion 1 (particle size 25 nm, silver 3.0 milligram atom, water solvent), ethanol 80 ml and water 20 ml, nitrogen was added at 50 mL / min. It heated to 40 degreeC, blowing in by the flow volume of. To this mixture was further added hydrazine monohydrate (7.5 g, 150 mmol). The reduction reaction was terminated by stirring for 2 hours while maintaining at 40 ° C.
実施例1のエタノール80mlと水20mlからなる混合物をイソプロピルアルコール80mlと水20mlからなる混合物にする以外は、実施例1と同様にして銀コア銅シェルナノ粒子分散体を作製した。 (Example 2) Solvent changed to isopropyl alcohol / water solvent Silver core as in Example 1 except that the mixture of 80 ml of ethanol and 20 ml of water was changed to a mixture of 80 ml of isopropyl alcohol and 20 ml of water. A copper shell nanoparticle dispersion was prepared.
実施例1のエタノール80mlと水20mlからなる混合物をエチレングリコール80mlと水20mlからなる混合物にする以外は、実施例1と同様にして銀コア銅シェルナノ粒子分散体を作製した。 (Example 3) The solvent was changed to an ethylene glycol / water solvent. A silver core was prepared in the same manner as in Example 1 except that the mixture of 80 ml of ethanol and 20 ml of water was changed to a mixture of 80 ml of ethylene glycol and 20 ml of water. A copper shell nanoparticle dispersion was prepared.
実施例1の銀ナノ粒子分散液1を銀ナノ粒子分散液2にすることと、エタノール80mlと水20mlからなる混合物をエタノール100mlにすることと、ヒドラジン1水和物(7.5g、150mmol)をヒドラジン1水和物(15g、300mmol)にする以外は、実施例1と同様にして銀コア銅シェルナノ粒子分散体を作製した。 (Example 4) The solvent was changed to ethanol, and the amount of hydrazine hydrate was increased to a 4-fold molar amount. The silver
実施例1のエタノール80mlと水20mlを、エタノール50mlと水50mlにする以外は、実施例1と同様にして銀コア銅シェルナノ粒子分散体を作製した。 (Example 5) The solvent was changed to a mixed solvent of ethanol / water (volume ratio 5/5). Silver in the same manner as in Example 1 except that 80 ml of ethanol and 20 ml of water in Example 1 were changed to 50 ml of ethanol and 50 ml of water. A core copper shell nanoparticle dispersion was prepared.
実施例1のエタノール80mlと水20mlを、エタノール10mlと水90mlにする以外は、実施例1と同様にして銀コア銅シェルナノ粒子分散体を作製した。 (Example 6) The solvent was changed to an ethanol / water (
実施例1のエタノール80mlと水20mlを、水100mlにする以外は、実施例1と同様にして銀コア銅シェルナノ粒子分散体を作製した。 (Example 7) The solvent was changed to water A silver core copper shell nanoparticle dispersion was prepared in the same manner as in Example 1 except that 80 ml of ethanol and 20 ml of water were changed to 100 ml of water.
実施例1のエタノール80mlと水20mlを、エタノール95mlにすることと、ヒドラジン水和物を添加する前に、10wt%水酸化カリウムエタノール溶液(5g、8.9mmol)を加えること、ヒドラジン1水和物(7.5g、150mmol)をヒドラジン1水和物(2.25g、45mmol)にすること以外は、実施例1と同様にして銀コア銅シェルナノ粒子分散体を作製した。 (Example 8) The solvent was changed to ethanol, potassium hydroxide was added, and hydrazine hydrate was changed to 0.6-fold mol. 80 ml of ethanol and 20 ml of water in Example 1 were changed to 95 ml of ethanol, and hydrazine hydrated. 10 wt% potassium hydroxide in ethanol solution (5 g, 8.9 mmol), hydrazine monohydrate (7.5 g, 150 mmol) to hydrazine monohydrate (2.25 g, 45 mmol) A silver core copper shell nanoparticle dispersion was prepared in the same manner as in Example 1 except that.
実施例1のエタノール80mlと水20mlを、エタノール95mlにすることと、ヒドラジン水和物を添加する前に、10wt%水酸化ナトリウム水溶液(5g、12.5mmol)を加えること、ヒドラジン1水和物(7.5g、150mmol)をヒドラジン1水和物(1.13g、23mmol)にすること以外は、実施例1と同様にして銀コア銅シェルナノ粒子分散体を作製した。 (Example 9) The solvent was changed to ethanol, an aqueous sodium hydroxide solution was added, and the hydrazine hydrate was changed to 0.3-fold moles. 80 ml of ethanol and 20 ml of water were changed to 95 ml of ethanol and hydrazine water was added. Before adding the hydrate, add 10 wt% aqueous sodium hydroxide solution (5 g, 12.5 mmol), hydrazine monohydrate (7.5 g, 150 mmol) to hydrazine monohydrate (1.13 g, 23 mmol) A silver core copper shell nanoparticle dispersion was prepared in the same manner as in Example 1 except that.
実施例1のエタノール80mlと水20mlを、エタノール95mlにすることと、銀ナノ粒子分散液1を銀ナノ粒子分散液3にすること、ヒドラジン水和物を添加する前に、10wt%水酸化ナトリウム水溶液(5g、12.5mmol)を加えること、ヒドラジン1水和物(7.5g、150mmol)をヒドラジン1水和物(1.13g、23mmol)にすること以外は、実施例1と同様にして銀コア銅シェルナノ粒子分散体を作製した。 (Example 10) The solvent was changed to ethanol, an aqueous sodium hydroxide solution was added, and the nucleating agent was changed to the silver nanoparticle dispersion 3. By changing the ethanol 80 ml and water 20 ml of Example 1 to 95 ml of ethanol,
硝酸銀(0.51g、3.0mmol)、上記合成例3で得たチオエーテル含有有機化合物(A-1)2.254g、エタノール85mlからなる混合物に、窒素を50mL/分の流量で吹き込みながら、40℃まで加熱した。この溶液にヒドラジン1水和物(0.023g、0.45mmol)及びエタノール10mlの混合物を30分かけて添加して銀ナノ粒子分散液を作製した。この反応液にさらに、酸化銅(I)(5.4g、37.5mmol)、及び10wt%水酸化ナトリウム水溶液(5g、12.5mmol)を加え、さらにヒドラジン1水和物(7.5g、150mmol)を加えた。40℃に保持したまま2時間攪拌し還元反応を終結させた。 (Example 11) The solvent was changed to ethanol, an aqueous sodium hydroxide solution was added, and the nucleating agent was prepared immediately before from silver nitrate. Silver nitrate (0.51 g, 3.0 mmol), the thioether-containing organic compound (A -1) A mixture consisting of 2.254 g and 85 ml of ethanol was heated to 40 ° C. while blowing nitrogen at a flow rate of 50 mL / min. To this solution, a mixture of hydrazine monohydrate (0.023 g, 0.45 mmol) and ethanol 10 ml was added over 30 minutes to prepare a silver nanoparticle dispersion. Further, copper (I) oxide (5.4 g, 37.5 mmol) and a 10 wt% aqueous sodium hydroxide solution (5 g, 12.5 mmol) were added to the reaction solution, and hydrazine monohydrate (7.5 g, 150 mmol) was further added. ) Was added. The reduction reaction was terminated by stirring for 2 hours while maintaining at 40 ° C.
実施例1の酸化銅(I)(5.4g、37.5mmol)を酸化銅(II)(6.0g、75mmol)にすることと、ヒドラジン1水和物(7.5g、150mmol)をヒドラジン1水和物(2.25g、45mmol)にすること以外は、実施例1と同様にして銀コア銅シェルナノ粒子分散体を作製した。 (Example 12) The copper raw material was changed to copper (II) oxide, and the hydrazine hydrate was changed to 0.6-fold molar amount. The copper oxide (I) (5.4 g, 37.5 mmol) of Example 1 was changed to copper oxide. Example II with the exception of (II) (6.0 g, 75 mmol) and hydrazine monohydrate (7.5 g, 150 mmol) to hydrazine monohydrate (2.25 g, 45 mmol). Similarly, a silver core copper shell nanoparticle dispersion was prepared.
実施例1の銀ナノ粒子分散液1(粒径25nm、銀3.0ミリグラム原子、水溶媒)の使用割合を銀7.0ミリグラム原子とすること以外は、実施例1と同様にして銀コア銅シェルナノ粒子分散体を作製した。 (Example 13) The nucleating agent usage ratio was changed to 7.0 milligram atoms of silver nanoparticles. The usage ratio of the
上記実施例で得られた銀コア銅シェルナノ粒子分散体をエチレングリコールで希釈し、希釈直後及び希釈1時間後にUV-Vis測定を行った。希釈直後と比べ希釈1時間後の波長575nmにおける吸収強度が、5%未満の減少率であれば耐酸化性良好、酸化が進行して5%より大きい減少率を示す時には耐酸化性不良とした。 Oxidation Resistance Evaluation Method The silver core copper shell nanoparticle dispersion obtained in the above examples was diluted with ethylene glycol, and UV-Vis measurement was performed immediately after dilution and 1 hour after dilution. If the absorption intensity at a wavelength of 575 nm after 1 hour of dilution is less than 5% compared to immediately after dilution, the oxidation resistance is good, and when the oxidation progresses and the decrease rate is greater than 5%, the oxidation resistance is poor. .
アルゴンを満たしたグローブバッグ中、上記実施例1~13で得られた複合体の水分散液を、7.6×1.3cmの清浄なスライドガラスの一端からおよそ0.5cm付近に約0.1mL程度滴下し、バーコーター(16番)を用いて展開して薄膜とした。そのまま、アルゴン雰囲気下で乾燥させた後、窒素を流通させた炉に移し、窒素雰囲気下で250℃30分間加熱した後、放冷した。スライドガラスを炉から取り出し、直ちに電気抵抗率を測定した。結果を表1に示した。 (Application Example 1) Preparation of thin film and measurement of specific resistance of thin film In a glove bag filled with argon, the aqueous dispersion of the composite obtained in Examples 1 to 13 was cleaned with a clean size of 7.6 × 1.3 cm. About 0.1 mL was dropped from one end of the slide glass to about 0.5 cm and developed using a bar coater (# 16) to form a thin film. After drying in an argon atmosphere as it was, it was transferred to a furnace in which nitrogen was circulated, heated in a nitrogen atmosphere at 250 ° C. for 30 minutes, and then allowed to cool. The glass slide was removed from the furnace and the electrical resistivity was measured immediately. The results are shown in Table 1.
実施例1~13で得られた複合体の水分散液体を、ポリプロピレン製密閉容器中室温で保存し、経時的に外観と動的光散乱法による粒子径分布を測定した。その結果、3月にわたってほとんど変化がなかった。詳細は表1にまとめて示した。 (Application Example 2) Storage stability of aqueous dispersions The aqueous dispersion liquids of the composites obtained in Examples 1 to 13 were stored at room temperature in a polypropylene sealed container, and the appearance and dynamic light scattering method were obtained over time. The particle size distribution was measured. As a result, there was little change over March. Details are summarized in Table 1.
実施例1のチオエーテル含有有機化合物(A-1)を比較合成例で得た高分子化合物(固形分2.254g)にする以外は、実施例1と同様にして銀コア銅シェルナノ粒子分散体を作製した。また得られた赤褐色の溶液を少量を採取し、エチレングリコールで希釈して、紫外可視吸収スペクトルを取得すると、ナノサイズの還元銅が示す565~580nmのプラズモン共鳴吸収のピークが観測された。さらに希釈から1時間経過後に紫外可視吸収スペクトルを取得すると、酸化によりプラズモン共鳴吸収のピークが減少することがわかった。 Comparative Example 1 Application of Comparative Methacrylate Copolymer to Silver Core Copper Shell Nanoparticle Synthesis Polymer Compound (Solid Content 2.254 g) Obtained from Comparative Synthesis Example of Thioether-Containing Organic Compound (A-1) of Example 1 A silver core copper shell nanoparticle dispersion was prepared in the same manner as in Example 1 except that. Further, when a small amount of the obtained reddish brown solution was collected and diluted with ethylene glycol to obtain an ultraviolet-visible absorption spectrum, a peak of plasmon resonance absorption at 565 to 580 nm indicated by nano-sized reduced copper was observed. Furthermore, when an ultraviolet-visible absorption spectrum was acquired after 1 hour from the dilution, it was found that the peak of plasmon resonance absorption decreased due to oxidation.
酸化銅(I)(5.4g、37.5mmol)、上記合成例3で得たチオエーテル含有有機化合物(A-1)(2.254g)、銀ナノ粒子分散液1(粒径25nm、銀1.5mmol、水溶媒)、酢酸エチル100mlからなる混合物に、窒素を50mL/分の流量で吹き込みながら、40℃まで加熱した。この混合物に、さらにヒドラジン1水和物(7.5g、150mmol)を加えた。40℃に保持したまま2時間攪拌したところ、容器の底に銅鏡が発生した。上澄み液をとり、紫外可視吸収スペクトルを測定したところ、570~600nmの間に観測されるピークは存在していないことを確認した。 (Comparative Example 2) Application of ethyl acetate to the synthesis of silver core copper shell nanoparticles Copper (I) oxide (5.4 g, 37.5 mmol), the thioether-containing organic compound (A-1) obtained in Synthesis Example 3 (2) 254 g), silver nanoparticle dispersion 1 (particle size 25 nm, silver 1.5 mmol, water solvent), and
市販の酸化銅(I)(5.4g、37.5mmol)、酢酸銀(0.31g、1.88mmol)、オクチルアミン(15ml)、ヘキサン(15ml)からなる混合物に、窒素を50mL/分の流量で吹き込みながら、40℃まで加熱した。この混合物に、さらにヒドラジン1水和物(7.5g、150mmol)を加えた。5分後に発熱及び黒色粉の生成が観察された。40℃に保持したまま2時間攪拌したところ、容器底に銅鏡及び沈殿を生じ、上澄みは透明になっていた。 (Comparative Example 3) Application of commercially available copper oxide to the method of JP 2008-19461 A Commercially available copper oxide (I) (5.4 g, 37.5 mmol), silver acetate (0.31 g, 1.88 mmol), A mixture composed of octylamine (15 ml) and hexane (15 ml) was heated to 40 ° C. while nitrogen was blown at a flow rate of 50 mL / min. To this mixture was further added hydrazine monohydrate (7.5 g, 150 mmol). After 5 minutes, exotherm and black powder formation were observed. When stirred for 2 hours while maintaining at 40 ° C., a copper mirror and precipitation were formed at the bottom of the container, and the supernatant was transparent.
上記比較例3において、合成例3で得たチオエーテル含有有機化合物(A-1)(2.254g)を加え、同様に実施したところ、容器底に銅鏡及び沈殿を生じ、上澄みは透明になっていた。 (Comparative Example 4) Application of commercially available copper oxide to the method of JP 2008-19461 A In the above Comparative Example 3, the thioether-containing organic compound (A-1) (2.254 g) obtained in Synthesis Example 3 was added, When carried out in the same manner, a copper mirror and precipitation were formed at the bottom of the container, and the supernatant was transparent.
酸化銅(I)(5.4g、37.5mmol)、チオエーテル含有有機化合物(A-1)(2.254g)、硝酸銀(0.51g、3mmol)、エタノール80mlと水20mlからなる混合物に、窒素を50mL/分の流量で吹き込みながら、40℃まで加熱した。この混合物に、さらにヒドラジン1水和物(7.5g、150mmol)を加えた。40℃に保持したまま2時間攪拌し還元反応を終結させた。その結果、黒色の沈殿物が生成した。 (Comparative Example 5) Simultaneous preparation of silver nitrate Copper (I) oxide (5.4 g, 37.5 mmol), thioether-containing organic compound (A-1) (2.254 g), silver nitrate (0.51 g, 3 mmol), ethanol 80 ml, The mixture consisting of 20 ml of water was heated to 40 ° C. while nitrogen was blown at a flow rate of 50 mL / min. To this mixture was further added hydrazine monohydrate (7.5 g, 150 mmol). The reduction reaction was terminated by stirring for 2 hours while maintaining at 40 ° C. As a result, a black precipitate was formed.
Claims (8)
- 下記一般式(1)
X-(OCH2CHR1)n-O-CH2-CH(OH)-CH2-S-Z (1)
〔式(1)中、XはC1~C8のアルキル基であり、R1は水素原子又はメチル基であり、nは2~100の繰り返し数を示す整数であって、R1は繰り返し単位ごとに独立し、同一であっても異なっていても良く、ZはC2~C12のアルキル基、アリル基、アリール基、アリールアルキル基、-R2-OH、-R2-NHR3、又は-R2-(COR4)m(但し、R2はC1~C4の飽和炭化水素基であり、R3は水素原子、C2~C4のアシル基、C2~C4のアルコキシカルボニル基、又は芳香環上にC1~C4のアルキル基又はC1~C8のアルコキシ基を置換基として有していても良いベンジルオキシカルボニル基であり、R4はヒドロキシ基、C1~C4のアルキル基又はC1~C8のアルコキシ基であり、mは1~3である。)で表される基である。〕
で表されるチオエーテル含有有機化合物(A)の存在下、
(i)銀ナノ粒子と酸化銅(I)及び/又は酸化銅(II)をヒドラジン系化合物と反応せずかつ当該ヒドラジン系化合物と相溶する溶媒と混合する工程と、
(ii)酸化銅(I)及び/又は酸化銅(II)を還元することで、銀ナノ粒子をコアとし、その周囲に銅をシェルとして生成させる工程と、
を有することを特徴とする有機化合物と銀コア銅シェルナノ粒子との複合体の製造方法。 The following general formula (1)
X— (OCH 2 CHR 1 ) n —O—CH 2 —CH (OH) —CH 2 —SZ (1)
[In the formula (1), X is a C 1 to C 8 alkyl group, R 1 is a hydrogen atom or a methyl group, n is an integer indicating a repeating number of 2 to 100, and R 1 is a repeating group. Each unit is independent and may be the same or different. Z is a C 2 to C 12 alkyl group, allyl group, aryl group, arylalkyl group, —R 2 —OH, —R 2 —NHR 3 Or —R 2 — (COR 4 ) m (where R 2 is a C 1 -C 4 saturated hydrocarbon group, R 3 is a hydrogen atom, a C 2 -C 4 acyl group, C 2 -C 4) Or a benzyloxycarbonyl group optionally having a C 1 -C 4 alkyl group or a C 1 -C 8 alkoxy group as a substituent on the aromatic ring, R 4 is a hydroxy group, Al of C 1 ~ C 4 alkyl or C 1 ~ C 8 An alkoxy group, m is a group represented by 1-3.). ]
In the presence of a thioether-containing organic compound (A) represented by
(I) mixing silver nanoparticles and copper (I) oxide and / or copper (II) with a solvent that does not react with the hydrazine compound and is compatible with the hydrazine compound;
(Ii) reducing copper oxide (I) and / or copper oxide (II) to form silver nanoparticles as a core and forming copper as a shell around the silver nanoparticles,
The manufacturing method of the composite_body | complex of the organic compound and silver core copper shell nanoparticle characterized by having. - 前記溶媒がアルコール、水単独及びこれらの混合溶剤からなる群から選ばれる一種である請求項1記載の製造方法。 The production method according to claim 1, wherein the solvent is a kind selected from the group consisting of alcohol, water alone and a mixed solvent thereof.
- 前記チオエーテル含有有機化合物(A)が、グリシジル基を末端に有するポリエーテル化合物(a1)とチオール化合物(a2)とを反応させて得られるものである請求項1又は2記載の製造方法。 The production method according to claim 1 or 2, wherein the thioether-containing organic compound (A) is obtained by reacting a glycidyl group-terminated polyether compound (a1) and a thiol compound (a2).
- 下記一般式(1)
X-(OCH2CHR1)n-O-CH2-CH(OH)-CH2-S-Z (1)
〔式(1)中、XはC1~C8のアルキル基であり、R1は水素原子又はメチル基であり、nは2~100の繰り返し数を示す整数であって、R1は繰り返し単位ごとに独立し、同一であっても異なっていても良く、ZはC2~C12のアルキル基、アリル基、アリール基、アリールアルキル基、-R2-OH、-R2-NHR3、又は-R2-(COR4)m(但し、R2はC1~C4の飽和炭化水素基であり、R3は水素原子、C2~C4のアシル基、C2~C4のアルコキシカルボニル基、又は芳香環上にC1~C4のアルキル基又はC1~C8のアルコキシ基を置換基として有していても良いベンジルオキシカルボニル基であり、R4はヒドロキシ基、C1~C4のアルキル基又はC1~C8のアルコキシ基であり、mは1~3である。)で表される基である。〕
で表されるチオエーテル含有有機化合物(A)と、銀コア銅シェルナノ粒子(B)とを含有することを特徴とする有機化合物と銀コア銅シェルナノ粒子との複合体。 The following general formula (1)
X— (OCH 2 CHR 1 ) n —O—CH 2 —CH (OH) —CH 2 —SZ (1)
[In the formula (1), X is a C 1 to C 8 alkyl group, R 1 is a hydrogen atom or a methyl group, n is an integer indicating a repeating number of 2 to 100, and R 1 is a repeating group. Each unit is independent and may be the same or different. Z is a C 2 to C 12 alkyl group, allyl group, aryl group, arylalkyl group, —R 2 —OH, —R 2 —NHR 3 Or —R 2 — (COR 4 ) m (where R 2 is a C 1 -C 4 saturated hydrocarbon group, R 3 is a hydrogen atom, a C 2 -C 4 acyl group, C 2 -C 4) Or a benzyloxycarbonyl group optionally having a C 1 -C 4 alkyl group or a C 1 -C 8 alkoxy group as a substituent on the aromatic ring, R 4 is a hydroxy group, Al of C 1 ~ C 4 alkyl or C 1 ~ C 8 An alkoxy group, m is a group represented by 1-3.). ]
The composite of the organic compound and silver core copper shell nanoparticle characterized by containing the thioether containing organic compound (A) represented by these, and silver core copper shell nanoparticle (B). - 前記チオエーテル含有有機化合物(A)が、グリシジル基を末端に有するポリエーテル化合物(a1)とチオール化合物(a2)とを反応させて得られるものである請求項4記載の複合体。 The composite according to claim 4, wherein the thioether-containing organic compound (A) is obtained by reacting a glycidyl group-terminated polyether compound (a1) and a thiol compound (a2).
- 前記複合体中のチオエーテル含有有機化合物(A)の含有率が2~8質量%である請求項4又は5記載の複合体。 6. The composite according to claim 4, wherein the content of the thioether-containing organic compound (A) in the composite is 2 to 8% by mass.
- 前記複合体が粒子状であり、透過型電子顕微鏡像で観測される100個の当該粒子の平均粒子径が20~50nmの範囲である請求項4~6の何れか1項記載の複合体。 The composite according to any one of claims 4 to 6, wherein the composite is in the form of particles, and an average particle diameter of 100 particles observed in a transmission electron microscope image is in the range of 20 to 50 nm.
- 請求項1~3の何れか1項記載の製造方法で得られるものである請求項4~7の何れか1項記載の複合体。 The composite according to any one of claims 4 to 7, which is obtained by the production method according to any one of claims 1 to 3.
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IT201800009521A1 (en) * | 2018-10-17 | 2020-04-17 | Li Volsi Lorenzo Marco | STABILIZING SUBSTANCE OF A AQUEOUS MIX AND METHOD FOR MAKING FILMS CONTAINING THIS STABILIZING SUBSTANCE |
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JP5077728B1 (en) | 2012-11-21 |
CN103328136A (en) | 2013-09-25 |
KR101495698B1 (en) | 2015-02-25 |
JPWO2012133296A1 (en) | 2014-07-28 |
CN103328136B (en) | 2014-12-03 |
KR20130056903A (en) | 2013-05-30 |
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