JP2006183072A - Silver particulate, method for producing the same and conductive paste containing silver particulate - Google Patents
Silver particulate, method for producing the same and conductive paste containing silver particulate Download PDFInfo
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 95
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 94
- 239000004332 silver Substances 0.000 title claims abstract description 94
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 45
- 239000002245 particle Substances 0.000 claims abstract description 42
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 claims abstract description 30
- -1 aliphatic primary amine Chemical class 0.000 claims abstract description 27
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 25
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 22
- 239000003960 organic solvent Substances 0.000 claims abstract description 14
- 239000011164 primary particle Substances 0.000 claims abstract description 6
- 239000010419 fine particle Substances 0.000 claims description 71
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 22
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 11
- 235000019253 formic acid Nutrition 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 8
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical compound [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 claims description 7
- 229940071536 silver acetate Drugs 0.000 claims description 7
- FAXDZWQIWUSWJH-UHFFFAOYSA-N 3-methoxypropan-1-amine Chemical compound COCCCN FAXDZWQIWUSWJH-UHFFFAOYSA-N 0.000 claims description 5
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 4
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 4
- WUGQZFFCHPXWKQ-UHFFFAOYSA-N Propanolamine Chemical compound NCCCO WUGQZFFCHPXWKQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000011668 ascorbic acid Substances 0.000 claims description 2
- 235000010323 ascorbic acid Nutrition 0.000 claims description 2
- 229960005070 ascorbic acid Drugs 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- SSJXIUAHEKJCMH-UHFFFAOYSA-N cyclohexane-1,2-diamine Chemical compound NC1CCCCC1N SSJXIUAHEKJCMH-UHFFFAOYSA-N 0.000 claims description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 2
- JKOCEVIXVMBKJA-UHFFFAOYSA-M silver;butanoate Chemical compound [Ag+].CCCC([O-])=O JKOCEVIXVMBKJA-UHFFFAOYSA-M 0.000 claims description 2
- CYLMOXYXYHNGHZ-UHFFFAOYSA-M silver;propanoate Chemical compound [Ag+].CCC([O-])=O CYLMOXYXYHNGHZ-UHFFFAOYSA-M 0.000 claims description 2
- 238000010304 firing Methods 0.000 abstract description 17
- 238000000034 method Methods 0.000 abstract description 17
- 239000002994 raw material Substances 0.000 abstract description 15
- 230000001747 exhibiting effect Effects 0.000 abstract description 5
- 239000000243 solution Substances 0.000 description 20
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- 239000007788 liquid Substances 0.000 description 8
- 239000011521 glass Substances 0.000 description 7
- 239000000758 substrate Substances 0.000 description 7
- 238000005259 measurement Methods 0.000 description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 229920000139 polyethylene terephthalate Polymers 0.000 description 4
- 239000005020 polyethylene terephthalate Substances 0.000 description 4
- 238000007639 printing Methods 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 238000004220 aggregation Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 3
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000010908 decantation Methods 0.000 description 3
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000006228 supernatant Substances 0.000 description 3
- 229940116411 terpineol Drugs 0.000 description 3
- QMGJMGFZLXYHCR-UHFFFAOYSA-N 1-(2-butoxypropoxy)butane Chemical compound CCCCOCC(C)OCCCC QMGJMGFZLXYHCR-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 2
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 2
- 239000011112 polyethylene naphthalate Substances 0.000 description 2
- 229920006290 polyethylene naphthalate film Polymers 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 150000003139 primary aliphatic amines Chemical class 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 230000007261 regionalization Effects 0.000 description 2
- 238000007650 screen-printing Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- OBETXYAYXDNJHR-SSDOTTSWSA-M (2r)-2-ethylhexanoate Chemical compound CCCC[C@@H](CC)C([O-])=O OBETXYAYXDNJHR-SSDOTTSWSA-M 0.000 description 1
- 229910013973 M18XHF22 Inorganic materials 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- YMHQVDAATAEZLO-UHFFFAOYSA-N cyclohexane-1,1-diamine Chemical compound NC1(N)CCCCC1 YMHQVDAATAEZLO-UHFFFAOYSA-N 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229920000768 polyamine Chemical class 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
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Abstract
Description
本発明は、銀微粒子及びその製造方法に関する。本発明はまた、該銀微粒子を含有する導電ペーストに関する。 The present invention relates to silver fine particles and a method for producing the same. The present invention also relates to a conductive paste containing the silver fine particles.
近年、銀微粒子は、電子部品の電極や回路パターンを形成するための導電ペーストの原料として多用されている。例えば、回路パターンは、通常、基板に、銀微粒子を含有する導電ペーストを使用して、スクリーン印刷で配線幅５０μｍ程度のパターンを印刷した後、５００℃以上の高温で焼成して形成される。 In recent years, silver fine particles have been widely used as a raw material for conductive paste for forming electrodes and circuit patterns of electronic components. For example, the circuit pattern is usually formed by printing a pattern having a wiring width of about 50 μm by screen printing on a substrate using a conductive paste containing silver fine particles, and then baking at a high temperature of 500 ° C. or higher.
最近では、携帯電話をはじめとする分野で、基板として、ポリイミド製フレキシブル回路基板の他、より安価なＰＥＴ（ポリエチレンテレフタレート）フィルムやＰＥＮ（ポリエチレンナフタレート）フィルム等を使用する動きがある。これらの基板との組み合わせでは、導電ペーストは、２００℃以下の低温で焼成可能であることが要求される。 Recently, in fields such as mobile phones, there is a movement to use a cheaper PET (polyethylene terephthalate) film, PEN (polyethylene naphthalate) film, or the like as a substrate in addition to a polyimide flexible circuit board. In combination with these substrates, the conductive paste is required to be baked at a low temperature of 200 ° C. or lower.
一方、サブミクロン以下の銀微粒子を製造する方法として、ガス中蒸発法、及び化学的還元法などの方法が知られている。しかし、これらの方法による銀微粒子を低温焼成用の導電ペーストの原料とする場合にはそれぞれ問題点を有していた。 On the other hand, methods such as a gas evaporation method and a chemical reduction method are known as methods for producing silver fine particles of submicron or less. However, each of these methods has its own problems when silver fine particles are used as a raw material for conductive paste for low-temperature firing.
ガス中蒸発法によれば、ナノレベルの単分散微粒子が得られるが、そのままでは凝集し易く不安定であるため、アミン等の分散剤を加え、安定化した分散液とすることが提案されている。しかし、この分散液を回路パターン等の形成に使用する場合、分散液中の分散剤の除去という新たな問題が生じ、結果として２００℃超での熱処理が必要となり、低温焼成用の導電ペーストの原料には不向きである（特許文献１参照）。 According to the gas evaporation method, nano-level monodispersed fine particles can be obtained. However, it is prone to agglomerate and is unstable as it is, and it has been proposed to add a dispersant such as amine to obtain a stabilized dispersion. Yes. However, when this dispersion is used for forming a circuit pattern or the like, a new problem of removal of the dispersant in the dispersion arises. As a result, heat treatment above 200 ° C. is required, and the conductive paste for low-temperature firing is required. Not suitable for raw materials (see Patent Document 1).
化学的還元法によれば、還元剤を添加して、金属化合物の水溶液中で金属を還元析出させることにより、ほぼ単分散に近い独立球状の金属微粒子が得られるが、実施例で調製されている銀微粒子は粒径が約１μｍと大きく、低温焼成用の導電ペーストの原料には不向きである（特許文献２参照）。 According to the chemical reduction method, by adding a reducing agent and reducing and precipitating a metal in an aqueous solution of a metal compound, independent spherical metal fine particles close to monodispersion can be obtained. The silver fine particles have a large particle size of about 1 μm and are not suitable as a raw material for conductive paste for low-temperature firing (see Patent Document 2).
また、結晶子径とタップ密度を規定した銀微粒子が提案されているが、これらは５００℃以上の高温焼成用の導電ペーストの原料に専ら適しており、低温焼成用の導電ペーストの原料には不向きである（特許文献３参照）。 In addition, silver fine particles having a defined crystallite size and tap density have been proposed, but these are suitable only as a raw material for conductive paste for high-temperature firing at 500 ° C. or higher, and as a raw material for conductive paste for low-temperature firing. It is unsuitable (refer patent document 3).
さらに、湿式還元法により製造され、平均粒子径と凝集度を規定した銀微粒子が提案されているが、印刷特性の点からも難点があり、低温焼成用の導電ペーストの原料には不向きである（特許文献４）。 Further, silver fine particles produced by a wet reduction method and having an average particle size and a specified degree of aggregation have been proposed, but there are disadvantages in terms of printing characteristics, and they are not suitable as a raw material for conductive paste for low-temperature firing. (Patent Document 4).
このように、実用的な条件下、２００℃以下の低温焼成で、導電回路が要求するような十分な導電性を示す導電ペースト用の原料となる銀微粒子は知られてなかった。
本発明の目的は、上記のような状況に対応して、２００℃以下の焼成温度で、十分な導電性を示す導電ペーストの原料用の銀微粒子及び該銀微粒子を含有する導電ペーストを提供することであり、また、該銀微粒子の製造方法を提供することである。 The object of the present invention is to provide a silver fine particle for a raw material of a conductive paste exhibiting sufficient conductivity at a firing temperature of 200 ° C. or less and a conductive paste containing the silver fine particle, corresponding to the above situation. In addition, the present invention provides a method for producing the silver fine particles.
本発明は、（ａ）１次粒子の平均粒子径が４０〜３５０nmであり、（ｂ）結晶子径が２０〜７０nmであり、かつ（ｃ）結晶子径に対する平均粒子径の比が１〜５である銀微粒子に関し、さらには該銀微粒子を含有する導電ペーストに関する。 In the present invention, (a) the average particle diameter of primary particles is 40 to 350 nm, (b) the crystallite diameter is 20 to 70 nm, and (c) the ratio of the average particle diameter to the crystallite diameter is 1 to Further, the present invention relates to a silver fine particle 5 and further to a conductive paste containing the silver fine particle.
また、本発明は、有機溶媒の存在又は非存在下に、カルボン酸の銀塩と脂肪族第一級アミンを混合し、次いで還元剤を添加して、反応温度２０〜８０℃で反応させて、銀微粒子を析出させることを含む銀微粒子の製造方法に関し、さらには該方法により得られた銀微粒子、及び該方法により得られた銀微粒子を含有する導電ペーストに関する。 In the present invention, a silver salt of a carboxylic acid and an aliphatic primary amine are mixed in the presence or absence of an organic solvent, a reducing agent is then added, and the reaction is performed at a reaction temperature of 20 to 80 ° C. Further, the present invention relates to a method for producing silver fine particles including depositing silver fine particles, and further relates to silver fine particles obtained by the method and a conductive paste containing the silver fine particles obtained by the method.
加えて、本発明は、（１）有機溶媒の存在又は非存在下に、カルボン酸の銀塩と脂肪族第一級アミンを混合する工程、（２）還元剤を添加して、反応温度２０〜８０℃で反応させる工程、及び（３）反応生成物を層分離させて、銀微粒子を含有する層を回収する工程を含む、導電ペーストの製造方法に関し、さらには該方法により得られた導電ペーストに関する。 In addition, the present invention includes (1) a step of mixing a silver salt of a carboxylic acid and an aliphatic primary amine in the presence or absence of an organic solvent, (2) a reducing agent is added, and a reaction temperature of 20 A process for reacting at ~ 80 ° C, and (3) a step of separating the reaction product and recovering a layer containing silver fine particles, and further comprising a process for producing a conductive paste, and further the conductive obtained by the method. Regarding paste.
本発明の銀微粒子は、導電ペーストの原料として有用であり、本発明の銀微粒子を含有する導電ペーストは、２００℃以下の焼成温度で、十分な導電性（例えば、比抵抗値１〜１０μΩｃｍレベル）を示す銀膜を形成することができる。また、本発明の銀微粒子は、平均粒子径が小さく、本発明の銀微粒子を含有する導電ペーストは、より微細化する回路パターン形成の要求にも応え得るものである。 The silver fine particles of the present invention are useful as a raw material for the conductive paste, and the conductive paste containing the silver fine particles of the present invention has sufficient conductivity (for example, a specific resistance value of 1 to 10 μΩcm level at a firing temperature of 200 ° C. or less. ) Can be formed. Further, the silver fine particles of the present invention have a small average particle diameter, and the conductive paste containing the silver fine particles of the present invention can meet the demand for circuit pattern formation to be further refined.
また、本発明の銀微粒子の製造方法は、大型の装置を使用することなく、効率よく、銀微粒子を製造することができ、ナノ銀粒子の最大かつ最終の課題ともいえる量産性への寄与が大きいものである。 Further, the method for producing silver fine particles of the present invention can efficiently produce silver fine particles without using a large apparatus, and contributes to mass productivity that can be said to be the largest and final problem of nano silver particles. It ’s a big one.
本発明の銀微粒子は、（ａ）１次粒子の平均粒子径が４０〜３５０nmであり、（ｂ）結晶子径が２０〜７０nmであり、かつ（ｃ）結晶子径に対する平均粒子径の比が１〜５であることを特徴とする、銀微粒子である。 In the silver fine particles of the present invention, (a) the average particle diameter of primary particles is 40 to 350 nm, (b) the crystallite diameter is 20 to 70 nm, and (c) the ratio of the average particle diameter to the crystallite diameter. Is a silver fine particle characterized by being 1-5.
本明細書において、平均粒子径は、レーザー回折散乱式粒度分布測定による、個数基準に基づく平均粒子径をいう。また、本明細書において、結晶子径は、ＣｕのＫα線を線源とした粉末Ｘ線回折法による測定から、面指数（１，１，１）面ピークの半値幅を求め、Ｓｃｈｅｒｒｅｒの式より計算した結果をいう。 In the present specification, the average particle diameter refers to an average particle diameter based on the number standard by laser diffraction scattering type particle size distribution measurement. Further, in this specification, the crystallite diameter is obtained by measuring the half width of the plane index (1,1,1) plane peak from the measurement by the powder X-ray diffraction method using Cu Kα ray as the source, and the Scherrer equation. The result calculated from
本発明の銀微粒子は、１次粒子の平均粒子径が４０〜３５０nmであり、好ましくは４０〜１００nmであり、より好ましくは５０〜８０nmである。なお、本発明の銀微粒子は通常、略球状である。その平均粒子径がこの範囲であると、銀微粒子の凝集が抑制され、導電ペースト化した場合に保存安定性が得られやすく、また微細回路パターン印刷用の導電ペーストの原料としても好適である。 In the silver fine particles of the present invention, the average particle diameter of primary particles is 40 to 350 nm, preferably 40 to 100 nm, and more preferably 50 to 80 nm. In addition, the silver fine particles of the present invention are generally spherical. When the average particle diameter is within this range, aggregation of silver fine particles is suppressed, and when it is made into a conductive paste, storage stability is easily obtained, and it is also suitable as a raw material for a conductive paste for printing a fine circuit pattern.
本発明の銀微粒子は、結晶子径が２０〜７０nmであり、好ましくは２０〜５０nmである。結晶子径がこの範囲であると、焼成時の体積収縮が抑制されるとともに、焼成後に形成される銀膜の緻密性や表面平滑性が確保され、精密な電子回路用途の導電ペーストの原料としても好適である。 The silver fine particles of the present invention have a crystallite diameter of 20 to 70 nm, preferably 20 to 50 nm. When the crystallite diameter is within this range, volume shrinkage during firing is suppressed, and the denseness and surface smoothness of the silver film formed after firing are ensured, and as a raw material for conductive pastes for precise electronic circuit applications Is also suitable.
本発明の銀微粒子は、１次銀微粒子の結晶子径に対する平均粒子径の比（平均粒子径／結晶子径）が１〜５であり、好ましくは１〜４であり、より好ましくは１〜３の範囲である。上記の比がこの範囲であると、２００℃以下の焼成温度で、十分な導電性を示す導電ペーストの原料用に好適である。 In the silver fine particles of the present invention, the ratio of the average particle size to the crystallite size of the primary silver fine particles (average particle size / crystallite size) is 1 to 5, preferably 1 to 4, more preferably 1 to 4. 3 range. When the above ratio is within this range, it is suitable for a raw material of a conductive paste exhibiting sufficient conductivity at a firing temperature of 200 ° C. or less.
本発明の銀微粒子は、カルボン酸の銀塩と脂肪族第一級アミンとを混合し、次いで還元剤を添加して、反応温度２０〜８０℃で銀微粒子を析出させることにより製造することができる。 The silver fine particles of the present invention can be produced by mixing a silver salt of a carboxylic acid and an aliphatic primary amine, then adding a reducing agent and precipitating the silver fine particles at a reaction temperature of 20 to 80 ° C. it can.
はじめに、カルボン酸の銀塩と脂肪族第一級アミンとを混合して、カルボン酸の銀塩を溶解させた溶液を得る。溶液中では、カルボン酸の銀塩に脂肪族第一級アミンが配位し、一種のアミン錯体を形成していると考えられる。 First, a silver salt of carboxylic acid and an aliphatic primary amine are mixed to obtain a solution in which the silver salt of carboxylic acid is dissolved. In solution, it is considered that an aliphatic primary amine is coordinated to a silver salt of carboxylic acid to form a kind of amine complex.
カルボン酸の銀塩は、脂肪族、芳香族いずれのカルボン酸の銀塩であってもよい。また、モノカルボン酸の銀塩であっても、ジカルボン酸等のポリカルボン酸の銀塩であってもよい。脂肪族カルボン酸の銀塩は、鎖状脂肪族カルボン酸の銀塩であっても、環状脂肪族カルボン酸の銀塩であってもよい。好ましくは鎖状脂肪族モノカルボン酸の銀塩であり、より好ましくは、酢酸銀、プロピオン酸銀又は酪酸銀であり、特に酢酸銀である。これらは、単独で、又は２種以上を併用することができる。 The silver salt of a carboxylic acid may be a silver salt of any aliphatic or aromatic carboxylic acid. Further, it may be a silver salt of monocarboxylic acid or a silver salt of polycarboxylic acid such as dicarboxylic acid. The silver salt of an aliphatic carboxylic acid may be a silver salt of a chain aliphatic carboxylic acid or a silver salt of a cyclic aliphatic carboxylic acid. Preferred is a silver salt of a chain aliphatic monocarboxylic acid, more preferred is silver acetate, silver propionate or silver butyrate, and particularly silver acetate. These can be used alone or in combination of two or more.
脂肪族第一級アミンは、鎖状脂肪族第一級アミンであっても、環状脂肪族第一級アミンであってもよい。また、モノアミン化合物であっても、ジアミン化合物等のポリアミン化合物であってもよい。脂肪族第一級アミンには、脂肪族炭化水素基が、ヒドロキシル基、メトキシ基、エトキシ基、プロピル基等のアルコキシ基、で置換されたものも含む。より好ましくは、３−メトキシプロピルアミン、３−アミノプロパノール及び１，２−ジアミノシクロヘキサンである。これらは、単独で、又は２種以上を併用することができる。 The aliphatic primary amine may be a chain aliphatic primary amine or a cyclic aliphatic primary amine. Moreover, even if it is a monoamine compound, polyamine compounds, such as a diamine compound, may be sufficient. Aliphatic primary amines include those in which an aliphatic hydrocarbon group is substituted with an alkoxy group such as a hydroxyl group, a methoxy group, an ethoxy group, or a propyl group. More preferred are 3-methoxypropylamine, 3-aminopropanol and 1,2-diaminocyclohexane. These can be used alone or in combination of two or more.
脂肪族第一級アミンの使用量は、生成する銀微粒子の後処理等プロセス上の要請や装置から決められるが、制御された粒子径の銀微粒子を得る点からは、カルボン酸の銀塩１当量に対して、１当量以上であることが好ましい。過剰な脂肪族第一級アミンの環境等への影響を考慮すると、１．０〜３．０当量であることが好ましく、より好ましくは１．０〜１．５当量、特に好ましくは１．０〜１．１当量である。特に、後続の工程で、還元剤によって銀微粒子を析出させた液をそのまま、導電ペーストとして使用する場合、過剰な脂肪族第一級アミンは加熱により気化する可能性があるため、上記の好ましい使用量の範囲を採用することがとりわけ望ましい。 The amount of the aliphatic primary amine used is determined by process requirements and equipment such as post-treatment of the silver fine particles to be produced. From the viewpoint of obtaining silver fine particles having a controlled particle size, the silver salt 1 of carboxylic acid is used. It is preferably 1 equivalent or more with respect to equivalents. Considering the influence of excess aliphatic primary amine on the environment, it is preferably 1.0 to 3.0 equivalents, more preferably 1.0 to 1.5 equivalents, particularly preferably 1.0. -1.1 equivalents. In particular, in the subsequent step, when the liquid in which silver fine particles are precipitated by a reducing agent is used as it is as a conductive paste, the above preferred use is possible because excess aliphatic primary amine may be vaporized by heating. It is particularly desirable to employ a range of quantities.
カルボン酸の銀塩と脂肪族第一級アミンとの混合は、有機溶媒の非存在下又は存在下に行うことができる。有機溶媒の使用により、混合を容易にすることができる。有機溶媒としては、エタノール、プロパノール、ブタノール等のアルコール類、プロピレングリコールジブチルエーテル等のエーテル類、トルエン等の芳香族炭化水素等が挙げられる。これらは、単独で、又は２種以上を併用することができる。有機溶媒の使用量は、混合の利便性、後続の工程での銀微粒子の生産性の点から、任意の量とすることができる。 Mixing of the silver salt of the carboxylic acid and the aliphatic primary amine can be performed in the absence or presence of an organic solvent. Mixing can be facilitated by the use of organic solvents. Examples of the organic solvent include alcohols such as ethanol, propanol and butanol, ethers such as propylene glycol dibutyl ether, and aromatic hydrocarbons such as toluene. These can be used alone or in combination of two or more. The amount of the organic solvent used can be set to an arbitrary amount from the viewpoint of convenience of mixing and productivity of silver fine particles in the subsequent steps.
カルボン酸塩の銀塩と脂肪族第一級アミンとの混合は、例えば、第一級脂肪族アミン、又は第一級脂肪族アミンと有機溶媒の混合物を攪拌しながら、カルボン酸の銀塩を添加して行う。添加終了後も、適宜、攪拌を続けることができる。その間、温度を、２０〜８０℃に維持することが好ましく、より好ましくは、２０〜６０℃である。 The mixing of the silver salt of the carboxylate and the aliphatic primary amine is performed, for example, by stirring the silver salt of the carboxylic acid while stirring the primary aliphatic amine or the mixture of the primary aliphatic amine and the organic solvent. Add and do. Stirring can be continued as appropriate even after the end of the addition. In the meantime, it is preferable to maintain temperature at 20-80 degreeC, More preferably, it is 20-60 degreeC.
その後、還元剤を添加して、銀微粒子を析出させる。還元剤としては、反応の制御の点から、ギ酸、ホルムアルデヒド、アスコルビン酸又はヒドラジンが好ましく、より好ましくは、ギ酸である。これらは単独で、又は２種以上を併用することができる。 Thereafter, a reducing agent is added to precipitate silver fine particles. As the reducing agent, formic acid, formaldehyde, ascorbic acid or hydrazine is preferable from the viewpoint of controlling the reaction, and formic acid is more preferable. These may be used alone or in combination of two or more.
還元剤の使用量は、通常、カルボン酸の銀塩に対して酸化還元当量以上であり、酸化還元当量が、０．５〜５倍であることが好ましく、より好ましくは１〜３倍である。カルボン酸の銀塩がモノカルボン酸の銀塩であり、還元剤としてギ酸を使用する場合、ギ酸のモル換算での使用量は、カルボン酸の銀塩１モルに対して、０．５〜１．５モルであることが好ましく、より好ましくは０．５〜１．０モル、さらに好ましくは０．５〜０．７５モルである。 The amount of the reducing agent used is usually at least a redox equivalent with respect to the silver salt of the carboxylic acid, and the redox equivalent is preferably 0.5 to 5 times, more preferably 1 to 3 times. . When the silver salt of carboxylic acid is a silver salt of monocarboxylic acid and formic acid is used as the reducing agent, the amount of formic acid used in terms of mole is 0.5 to 1 with respect to 1 mole of silver salt of carboxylic acid. 0.5 mol is preferable, more preferably 0.5 to 1.0 mol, and still more preferably 0.5 to 0.75 mol.
還元剤の添加及びその後の反応においては、温度を２０℃〜８０℃に維持する。温度は、２０〜７０℃であることが好ましく、より好ましくは、２０〜６０℃である。温度がこの範囲にあると、銀微粒子の粒成長が十分であり、生産性も高く、また二次凝集も抑制される。還元剤の添加及びその後の反応に要する時間は、反応装置の規模に依存するが、通常、１０分〜１０時間である。なお、還元剤の添加及びその後の反応に際して、必要に応じて、エタノール、プロパノール、ブタノール等のアルコール類、プロピレングリコールジブチルエーテル等のエーテル類、トルエン等の芳香族炭化水素等の有機溶媒を追加で添加することができる。 In the addition of the reducing agent and the subsequent reaction, the temperature is maintained between 20 ° C and 80 ° C. It is preferable that temperature is 20-70 degreeC, More preferably, it is 20-60 degreeC. When the temperature is within this range, the grain growth of silver fine particles is sufficient, the productivity is high, and secondary aggregation is also suppressed. The time required for the addition of the reducing agent and the subsequent reaction depends on the scale of the reaction apparatus, but is usually 10 minutes to 10 hours. In addition, in the addition of the reducing agent and the subsequent reaction, an organic solvent such as an alcohol such as ethanol, propanol or butanol, an ether such as propylene glycol dibutyl ether, or an aromatic hydrocarbon such as toluene is added as necessary. Can be added.
還元剤の添加及びその後の反応においては、カルボン酸の銀塩と脂肪族第一級アミンとを混合した溶液、還元剤、及び任意の有機溶媒の合計の容積（Ｌ）に対する、カルボン酸の銀塩の量（mol）が、１．０〜６．０mol／Ｌの範囲となるようにすることが好ましく、より好ましくは、２．０〜５．０mol／Ｌ、さらに好ましくは２．０〜４．０mol／Ｌである。濃度がこの範囲にあると、反応液の攪拌を十分行い、反応熱を除去することができるため、析出する銀微粒子の平均粒子径が適切となり、ひいては後続する工程での沈降デカント、溶媒置換等の操作に支障を来すこともない。 In the addition of the reducing agent and the subsequent reaction, the silver of the carboxylic acid with respect to the total volume (L) of the mixed solution of the silver salt of the carboxylic acid and the aliphatic primary amine, the reducing agent, and any organic solvent. The amount (mol) of the salt is preferably in the range of 1.0 to 6.0 mol / L, more preferably 2.0 to 5.0 mol / L, still more preferably 2.0 to 4 0.0 mol / L. If the concentration is within this range, the reaction solution can be sufficiently stirred and the heat of reaction can be removed, so that the average particle size of the precipitated silver fine particles becomes appropriate. As a result, precipitation decantation, solvent replacement, etc. in subsequent steps It will not interfere with the operation.
反応容器にカルボン酸の銀塩と脂肪族第一級アミンとを混合した溶液と任意の有機溶媒を仕込み、還元剤を連続的に供給するセミバッチ方式で反応を行った場合、カルボン酸の銀塩と脂肪族第一級アミンとを混合した溶液、還元剤及び任意の有機溶媒の合計の容積１Ｌにつき、還元剤の添加開始から反応終了までの所要時間１時間当たりの銀微粒子の析出量は、０．３〜１．０mol／ｈ／Ｌの範囲とすることができ、生産性は非常に大きい。連続式反応方式（連続式完全混合糟や流通式）で反応を実施した場合はさらに大きな生産性が得られ、工業的実施に対して大きな利得を与える。 When a reaction vessel is charged with a solution in which a silver salt of a carboxylic acid and an aliphatic primary amine are mixed and an arbitrary organic solvent, and the reaction is carried out in a semi-batch system in which a reducing agent is continuously supplied, the silver salt of the carboxylic acid The amount of silver fine particles deposited per hour per hour from the start of addition of the reducing agent to the end of the reaction per 1 L of the total volume of the solution, the reducing agent, and an arbitrary organic solvent mixed with the aliphatic primary amine, It can be in the range of 0.3 to 1.0 mol / h / L, and the productivity is very large. When the reaction is carried out by a continuous reaction system (continuous complete mixing tank or flow system), a greater productivity can be obtained, which gives a large gain to industrial implementation.
このようにして得られる銀微粒子は粒度分布が狭く、幾何標準偏差を２．０以下とすることができる。本明細書において、幾何標準偏差は、レーザー回折散乱式散乱式粒度分布測定による、個数基準の５０％粒子径（Ｄ５０値）に対する、８４．３％粒子径（Ｄ８４．３値）の比（Ｄ８４．３値／Ｄ５０値）をいう。 The silver fine particles obtained in this way have a narrow particle size distribution and a geometric standard deviation of 2.0 or less. In the present specification, the geometric standard deviation is the ratio (D84) of the 84.3% particle diameter (D84.3 value) to the 50% particle diameter (D50 value) based on the number measured by the laser diffraction scattering type particle size distribution measurement. .3 value / D50 value).
反応により析出した銀微粒子は沈降させて、デカンテーション等により上澄みを除去するか、又はメタノール、エタノール、テレピネオール等のアルコール等の溶媒を添加して分取することができる。銀微粒子を含む層はそのまま、導電ペーストとして使用することができる。導電ペーストは、導電ペースト中の銀含有率を４０〜９０重量％とすることが好ましく、より好ましくは４５〜８０重量％である。 Silver fine particles precipitated by the reaction can be settled and the supernatant removed by decantation or the like, or a solvent such as alcohol such as methanol, ethanol or terpineol can be added and fractionated. The layer containing silver fine particles can be used as a conductive paste as it is. The conductive paste preferably has a silver content in the conductive paste of 40 to 90% by weight, more preferably 45 to 80% by weight.
導電ペーストを、基材等に、スクリーン印刷等の従来公知の方法で印刷又は塗布した後、焼成することにより銀膜を形成することができる。焼成温度は、好ましくは、６０〜２００℃であり、より好ましくは６０〜１５０℃である。このようにして得られる銀膜は、十分な導電性（例えば、比抵抗値１〜１０μΩcmレベル）を示す。また、配合された銀微粒子の平均粒子径が小さく、より微細化する回路パターン形成への要求にも応え得るものである。 A silver film can be formed by printing or applying a conductive paste on a substrate or the like by a conventionally known method such as screen printing and then baking. The firing temperature is preferably 60 to 200 ° C, more preferably 60 to 150 ° C. The silver film thus obtained exhibits sufficient conductivity (for example, a specific resistance value of 1 to 10 μΩcm level). Moreover, the average particle diameter of the compounded silver fine particles is small, and it can meet the demand for circuit pattern formation to be further refined.
以下、実施例及び比較例によって、本発明を更に詳細に説明する。本発明は、これらの実施例に限定されるものではない。 Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. The present invention is not limited to these examples.
実施例１
１０Ｌのガラス製反応容器に３−メトキシプロピルアミン３．０kg（３０．９mol）を入れた。撹拌しながら、反応温度を４５℃以下に保持しつつ、酢酸銀５．０kg（３０．０mol）を添加した。添加直後は、透明な溶液となり溶解していくが、添加が進むにつれ溶液が次第に濁り、全量を添加すると灰茶濁色の粘調溶液となった。そこへ９５重量％のギ酸１．０kg（２１．０mol）をゆっくり滴下した。滴下直後から激しい発熱が認められたが、その間、反応温度を３０〜４５℃に保持した。当初、灰濁色の粘調溶液が、茶色から黒色へ変化した。全量を滴下した後反応を終了させた。反応混合物を４０℃で静置すると二層に分かれた。上層は黄色の透明な液であり、下層には黒色の銀微粒子が沈降した。上層の液には、銀成分が含まれていなかった。上層の液をデカンテーションで除去し、メタノールを使用して層分離させて銀含有率６５重量％の導電ペーストを得た。ギ酸の滴下開始から反応終了までに要した時間は６時間であった。また、反応容積当たり銀微粒子の生産性は、０．５７mol／ｈ／Ｌであった。なお、銀含有率は、導電ペースト約３ｇをルツボに採取し精秤した後、電気炉を使用し、８００℃で０．５時間焼成して有機成物を除去して重量を測定し、算定した値である。以下も同様とする。
Example 1
In a 10 L glass reaction vessel, 3.0 kg (30.9 mol) of 3-methoxypropylamine was placed. While stirring, the reaction temperature was maintained at 45 ° C. or lower, and 5.0 kg (30.0 mol) of silver acetate was added. Immediately after the addition, the solution became a transparent solution and dissolved, but as the addition proceeded, the solution gradually became turbid, and when the entire amount was added, it became an ash brown cloudy viscous solution. To this, 1.0 kg (21.0 mol) of 95% by weight formic acid was slowly added dropwise. Vigorous exotherm was observed immediately after the addition, while the reaction temperature was maintained at 30 to 45 ° C. Initially, the turbid viscous solution changed from brown to black. The reaction was terminated after the entire amount was added dropwise. The reaction mixture was allowed to stand at 40 ° C. and separated into two layers. The upper layer is a yellow transparent liquid, and black silver fine particles settled in the lower layer. The upper layer liquid did not contain a silver component. The upper layer liquid was removed by decantation, and the layers were separated using methanol to obtain a conductive paste having a silver content of 65% by weight. The time required from the start of formic acid dropping to the end of the reaction was 6 hours. The productivity of silver fine particles per reaction volume was 0.57 mol / h / L. The silver content is calculated by collecting approximately 3g of conductive paste in a crucible, weighing it accurately, using an electric furnace, firing at 800 ° C for 0.5 hours to remove organic components and measuring the weight. It is the value. The same applies to the following.
実施例２
１０Ｌのガラス製反応容器に３−メトキシプロピルアミン４．０kg（４５．０mol）を入れた。撹拌しながら、反応温度を４５℃以下に保持しつつ、酢酸銀５．０kg（３０．０mol）を添加した。添加直後は、透明な溶液となり溶解していくが、添加が進むにつれ溶液が次第に濁り、全量を添加すると灰茶濁色の粘調溶液となった。そこへ９５重量％のギ酸１．０kg（２１．０mol）をゆっくり滴下した。滴下直後から激しい発熱が認められたが、その間、反応温度を３０〜４５℃に保持した。当初、灰濁色の粘調溶液が茶色から黒色へ変化した。全量を滴下した後反応を終了させた。反応混合物を４０℃で静置すると二層に分かれた。上層は黄色の透明な液であり、下層には黒色の銀粒子が沈降した。上層の液には、銀成分が含まれていなかった。上層の液をデカンテーションし、メタノールを使用して層分離させて銀含有率６５重量％の導電ペーストを得た。ギ酸の滴下開始から反応終了反応に要した時間は６時間であった。反応容積あたりの銀微粒子の生産性は０．５０mol／ｈ／Ｌであった。
Example 2
In a 10 L glass reaction vessel, 4.0 kg (45.0 mol) of 3-methoxypropylamine was placed. While stirring, the reaction temperature was maintained at 45 ° C. or lower, and 5.0 kg (30.0 mol) of silver acetate was added. Immediately after the addition, the solution became a transparent solution and dissolved, but as the addition proceeded, the solution gradually became turbid, and when the entire amount was added, it became an ash brown cloudy viscous solution. To this, 1.0 kg (21.0 mol) of 95% by weight formic acid was slowly added dropwise. Vigorous exotherm was observed immediately after the addition, while the reaction temperature was maintained at 30 to 45 ° C. Initially, the turbid viscous solution changed from brown to black. The reaction was terminated after the entire amount was added dropwise. The reaction mixture was allowed to stand at 40 ° C. and separated into two layers. The upper layer was a yellow transparent liquid, and black silver particles were precipitated in the lower layer. The upper layer liquid did not contain a silver component. The upper layer liquid was decanted and the layers were separated using methanol to obtain a conductive paste having a silver content of 65% by weight. The time required for the reaction completion reaction from the start of formic acid dropping was 6 hours. The productivity of silver fine particles per reaction volume was 0.50 mol / h / L.
実施例３
１０Ｌのガラス製反応容器にトルエン１．５kgを入れ、ジアミノシクロヘキサン０．９kg（８．０mol）と２−エチルヘキサン酸０．８kg（５．５mol）を添加した後、攪拌しながら、反応温度を４５℃以下に保持しつつ、酢酸銀２．５kg（１５．０mol）を添加した。反応系がほぼ均一になったことを確認した後、急激に攪拌しながら、ギ酸０．５kg（１０．５mol）を少量ずつ、３時間かけて添加した。その間、反応温度を４０〜４５℃に保持した。その後、温度を４０〜４５℃に保持しつつ、２時間攪拌を続けて反応を終了させた。得られたペースト１kgに、メタノール０．３kgを加えて撹拌後、静置して上澄みを除去した。上澄みを除去したペーストに、テレピネオール４０ｇを加え、エバポレータで残存するメタノールを留去して、銀含有率６４％の導電ペーストを得た。反応容積あたりの銀微粒子の生産性は０．７９mol／ｈ／Ｌであった。
Example 3
Into a 10 L glass reaction vessel, 1.5 kg of toluene was added, 0.9 kg (8.0 mol) of diaminocyclohexane and 0.8 kg (5.5 mol) of 2-ethylhexanoic acid were added, and the reaction temperature was adjusted while stirring. While maintaining the temperature at 45 ° C. or lower, 2.5 kg (15.0 mol) of silver acetate was added. After confirming that the reaction system was almost uniform, 0.5 kg (10.5 mol) of formic acid was added in small portions over 3 hours with rapid stirring. Meanwhile, the reaction temperature was kept at 40-45 ° C. Thereafter, stirring was continued for 2 hours while maintaining the temperature at 40 to 45 ° C. to complete the reaction. To 1 kg of the obtained paste, 0.3 kg of methanol was added and stirred, and then allowed to stand to remove the supernatant. 40 g of terpineol was added to the paste from which the supernatant had been removed, and the remaining methanol was distilled off with an evaporator to obtain a conductive paste having a silver content of 64%. The productivity of silver fine particles per reaction volume was 0.79 mol / h / L.
比較例１
１０Ｌのガラス製反応容器に３−メトキシプロピルアミン３．０kg（３０．９mol）を入れた。撹拌しながら、液温を５０℃にして酢酸銀５．０kg（３０．０mol）を添加した。添加直後は、透明な溶液となり溶解していくが、添加が進むにつれ溶液が次第に濁り、全量を添加すると灰色の粒子の析出のある溶液となった。そこへ９５重量％のギ酸１．０kg（２１．０mol）を３時間かけて滴下した。滴下直後から激しい発熱が認められ、反応温度は９０℃に上昇した。激しく反応し、溶液の一部が反応容器から吹きこぼれた。その反応混合物は、大きな銀の凝集体を形成していて不均一であった。
Comparative Example 1
In a 10 L glass reaction vessel, 3.0 kg (30.9 mol) of 3-methoxypropylamine was placed. While stirring, the liquid temperature was adjusted to 50 ° C., and 5.0 kg (30.0 mol) of silver acetate was added. Immediately after the addition, the solution became a transparent solution and dissolved, but as the addition proceeded, the solution gradually became turbid, and when the entire amount was added, a solution with gray particles precipitated. Thereto was added dropwise 1.0 kg (21.0 mol) of 95% by weight of formic acid over 3 hours. Severe exotherm was observed immediately after the addition, and the reaction temperature rose to 90 ° C. It reacted vigorously and part of the solution spilled out of the reaction vessel. The reaction mixture was heterogeneous, forming large silver aggregates.
実施例１、２及び３について、日本電子製ＪＳＭ−５６００を用いて、倍率４０，０００倍でＳＥＭ写真を撮影した。結果を図１に示す。 For Examples 1, 2, and 3, SEM photographs were taken at a magnification of 40,000 times using JSM-5600 manufactured by JEOL. The results are shown in FIG.
実施例１、２及び３について、粒子特性、体積抵抗率及び保存安定性を測定・評価した。結果を表１に示す。 For Examples 1, 2, and 3, particle characteristics, volume resistivity, and storage stability were measured and evaluated. The results are shown in Table 1.
測定・評価は、次のようにして行った。 Measurement and evaluation were performed as follows.
平均粒子径及び幾何標準偏差：各実施例の導電ペースト約０．５ｇ）を、分散水(AEROSOL０．５％含有水)５０ｃｃに添加し、超音波分散機で５分間分散する。分散試料を、ベックマン・コールター社製の3（ＬＳ２３０）により測定した。個数基準に基づき、平均粒子径、１０％粒子径（Ｄ１０値）、２５％粒子径（Ｄ２５値）、５０％粒子径（Ｄ５０値）、７５％粒子径（Ｄ７５値）、９０％粒子径（Ｄ９０値）、８４．３％粒子径（Ｄ８４．３値）を測定し、さらに幾何標準偏差（５０％粒子径（Ｄ５０値）に対する８４．３％粒子径（Ｄ８４．３値）の比）を求めた。 Average particle diameter and geometric standard deviation: About 0.5 g of the conductive paste of each example) is added to 50 cc of dispersed water (water containing 0.5% of AEROSOL), and dispersed with an ultrasonic disperser for 5 minutes. The dispersion sample was measured by 3 (LS230) manufactured by Beckman Coulter. Based on the number standard, the average particle size, 10% particle size (D10 value), 25% particle size (D25 value), 50% particle size (D50 value), 75% particle size (D75 value), 90% particle size ( D90 value), 84.3% particle diameter (D84.3 value), and geometric standard deviation (ratio of 84.3% particle diameter (D84.3 value) to 50% particle diameter (D50 value)) Asked.
結晶子径：マックサイエンス社製Ｘ線回折測定装置（Ｍ１８ＸＨＦ２２）による測定によって、ＣｕのＫα線を線源とした面指数（１，１，１）面ピークの半値幅を求め、Ｓｃｈｅｒｒｅｒの式より結晶子径を計算した。 Crystallite diameter: The half-value width of the plane index (1,1,1) plane peak using Cu Kα ray as the radiation source was determined by measurement with an X-ray diffraction measurement device (M18XHF22) manufactured by Mac Science, and the Scherrer equation was used. The crystallite size was calculated.
体積抵抗率：各実施例の導電ペーストを用い、幅１．０mm・長さ６６mmのパターン回路を、約５μｍの厚みでガラス基板にスクリーン印刷して、実施例１及び２は、１５０℃で１０分、実施例３は、２００℃で２０分熱処理した後、抵抗値と厚さを測定して求めた。 Volume resistivity: Using the conductive paste of each example, a pattern circuit having a width of 1.0 mm and a length of 66 mm was screen-printed on a glass substrate with a thickness of about 5 μm. Example 3 was obtained by measuring the resistance value and thickness after heat treatment at 200 ° C. for 20 minutes.
保存安定性：各実施例の導電ペーストをガラス容器に入れて密封し、４０℃の恒温槽中に３ケ月間保存し流動性の変化を目視で観察した。
○：変化なし、△：やや悪くなった（実用上問題なし）、×：悪い（使用不可能）
Storage stability: The conductive paste of each example was sealed in a glass container, stored in a constant temperature bath at 40 ° C. for 3 months, and the change in fluidity was visually observed.
○: No change, △: Slightly worse (no problem in practical use), ×: Bad (unusable)
実施例４〜８
実施例１で得られた導電ペーストを、表２の条件で焼成して、上述の方法により体積抵抗率を測定した。結果を表２に示す。また、実施例７の焼成面を日本電子製 ＪＳＭ−５６００を用いて、倍率２０，０００倍でＳＥＭ写真を撮影した。結果を図２に示す。
Examples 4-8
The conductive paste obtained in Example 1 was fired under the conditions shown in Table 2, and the volume resistivity was measured by the method described above. The results are shown in Table 2. Further, an SEM photograph was taken of the fired surface of Example 7 at a magnification of 20,000 using JSM-5600 manufactured by JEOL. The results are shown in FIG.
実施例９〜１４
脂肪族第１級アミン、カルボン酸の銀塩、還元剤、還元剤添加後の反応温度及び反応時間を表３に示す組み合わせとした他は、実施例１と同様にして、実施例９〜１４の導電ペーストを調製し、粒子特性、体積抵抗及び保存安定性を測定した。測定の方法は上述のとおりであるが、体積抵抗率測定のための焼成は、１５０℃１０分の条件で行った。
Examples 9-14
Examples 9 to 14 were carried out in the same manner as in Example 1 except that the aliphatic primary amine, silver salt of carboxylic acid, reducing agent, reaction temperature and reaction time after addition of the reducing agent were combined as shown in Table 3. A conductive paste was prepared, and particle characteristics, volume resistance and storage stability were measured. The measurement method is as described above, but the firing for volume resistivity measurement was performed at 150 ° C. for 10 minutes.
比較例２
特開２００４−１０００１３号公報の第１実施形態を実施して、銀微粒子を得た。この銀微粒子を乾燥させずにメタノール洗浄した後、実施例３と同様にして、テレピネオール６０ｇを用いて溶媒置換をした。得られたペーストをスクリーン印刷しようとしたところ、印刷ができない状態だった。このペーストをニードル（１５Ｇ）からガラス基板に吐出後、２００℃で２０分焼成した。均一な銀膜にならないため、体積固有抵抗の測定ができなかった。
Comparative Example 2
The first embodiment of Japanese Patent Application Laid-Open No. 2004-100013 was performed to obtain silver fine particles. After washing the silver fine particles with methanol without drying, the solvent was replaced with 60 g of terpineol in the same manner as in Example 3. When I tried to screen print the resulting paste, I couldn't print. This paste was discharged from a needle (15G) onto a glass substrate and then baked at 200 ° C. for 20 minutes. Since the silver film was not uniform, the volume resistivity could not be measured.
本発明の銀微粒子を原料とした導電ペーストによれば、２００℃以下の焼成温度で、十分な導電性を示す銀幕を形成することができる。これは、現在、携帯電話をはじめとする分野で、基板として、ポリイミド製フレキシブル回路基板から、さらにより安価なＰＥＴ（ポリエチレンテレフタレート）フィルムやＰＥＮ（ポリエチレンナフタレート）フィルム等に変更したいという市場要求に応えるものである。本発明の銀微粒子の製造方法は、量産性能に優れ、従来の導電ペースト分野を一変しうるものであり、産業上の極めて有用なものである。 According to the conductive paste using the silver fine particles of the present invention as a raw material, a silver screen exhibiting sufficient conductivity can be formed at a firing temperature of 200 ° C. or lower. This is due to market demands in the field of cellular phones and the like that it is desired to change the substrate from a polyimide flexible circuit board to a cheaper PET (polyethylene terephthalate) film or PEN (polyethylene naphthalate) film. It is a response. The method for producing silver fine particles of the present invention is excellent in mass production performance, can completely change the conventional conductive paste field, and is extremely useful in industry.
Claims (12)
（ｂ）結晶子径が２０〜７０nmであり、かつ
（ｃ）結晶子径に対する平均粒子径の比が１〜５である
銀微粒子。 (A) The average particle diameter of the primary particles is 40 to 350 nm,
(B) Silver fine particles having a crystallite diameter of 20 to 70 nm and (c) a ratio of an average particle diameter to a crystallite diameter of 1 to 5.
（ｂ）結晶子径が２０〜５０nmであり、かつ
（ｃ）結晶子径に対する平均粒子径の比が１〜４である
請求項１記載の銀微粒子。 (A) The average particle diameter of the primary particles is 50 to 80 nm,
Silver fine particles according to claim 1, wherein (b) the crystallite diameter is 20 to 50 nm, and (c) the ratio of the average particle diameter to the crystallite diameter is 1 to 4.
（２）還元剤を添加して、反応温度２０〜８０℃で反応させる工程、及び
（３）反応生成物を層分離させて、銀微粒子を含有する層を回収する工程
を含む、導電ペーストの製造方法。 (1) A step of mixing a silver salt of a carboxylic acid and an aliphatic primary amine in the presence or absence of an organic solvent,
(2) a step of adding a reducing agent to react at a reaction temperature of 20 to 80 ° C., and (3) separating the reaction product into layers and recovering a layer containing silver fine particles. Production method.
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