JP6104760B2 - Method for producing metal nanoparticles - Google Patents
Method for producing metal nanoparticles Download PDFInfo
- Publication number
- JP6104760B2 JP6104760B2 JP2013179366A JP2013179366A JP6104760B2 JP 6104760 B2 JP6104760 B2 JP 6104760B2 JP 2013179366 A JP2013179366 A JP 2013179366A JP 2013179366 A JP2013179366 A JP 2013179366A JP 6104760 B2 JP6104760 B2 JP 6104760B2
- Authority
- JP
- Japan
- Prior art keywords
- metal
- metal ion
- liquid
- metal nanoparticles
- ion
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000002082 metal nanoparticle Substances 0.000 title claims description 86
- 238000004519 manufacturing process Methods 0.000 title claims description 20
- 229910021645 metal ion Inorganic materials 0.000 claims description 83
- 239000007788 liquid Substances 0.000 claims description 69
- 239000011163 secondary particle Substances 0.000 claims description 27
- 238000002156 mixing Methods 0.000 claims description 19
- -1 silver ions Chemical class 0.000 claims description 18
- 239000003638 chemical reducing agent Substances 0.000 claims description 15
- 239000002270 dispersing agent Substances 0.000 claims description 15
- 102000008186 Collagen Human genes 0.000 claims description 13
- 108010035532 Collagen Proteins 0.000 claims description 13
- 229920001436 collagen Polymers 0.000 claims description 13
- 108090000765 processed proteins & peptides Proteins 0.000 claims description 12
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 8
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 7
- 229910001431 copper ion Inorganic materials 0.000 claims description 7
- 229910052763 palladium Inorganic materials 0.000 claims description 6
- 229910052709 silver Inorganic materials 0.000 claims description 3
- 239000004332 silver Substances 0.000 claims description 3
- 239000006185 dispersion Substances 0.000 description 20
- 239000000243 solution Substances 0.000 description 20
- 238000006243 chemical reaction Methods 0.000 description 19
- 238000000034 method Methods 0.000 description 19
- 229910052751 metal Inorganic materials 0.000 description 16
- 239000002184 metal Substances 0.000 description 16
- 239000002904 solvent Substances 0.000 description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000002245 particle Substances 0.000 description 12
- 239000002994 raw material Substances 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 9
- 125000004429 atom Chemical group 0.000 description 8
- 229910052802 copper Inorganic materials 0.000 description 8
- 239000010949 copper Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 239000008139 complexing agent Substances 0.000 description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 7
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
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- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- 238000005227 gel permeation chromatography Methods 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 4
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- 108010010803 Gelatin Proteins 0.000 description 3
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- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
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- 125000003277 amino group Chemical group 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- FGJLAJMGHXGFDE-UHFFFAOYSA-L disodium;2,3-dihydroxybutanedioate;dihydrate Chemical compound O.O.[Na+].[Na+].[O-]C(=O)C(O)C(O)C([O-])=O FGJLAJMGHXGFDE-UHFFFAOYSA-L 0.000 description 3
- 238000002296 dynamic light scattering Methods 0.000 description 3
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- 235000011852 gelatine desserts Nutrition 0.000 description 3
- 239000000463 material Substances 0.000 description 3
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- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000003002 pH adjusting agent Substances 0.000 description 3
- MUJIDPITZJWBSW-UHFFFAOYSA-N palladium(2+) Chemical compound [Pd+2] MUJIDPITZJWBSW-UHFFFAOYSA-N 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 3
- 239000003223 protective agent Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000012279 sodium borohydride Substances 0.000 description 3
- 229910000033 sodium borohydride Inorganic materials 0.000 description 3
- 229940092162 sodium tartrate dihydrate Drugs 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 description 2
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 2
- SZNYYWIUQFZLLT-UHFFFAOYSA-N 2-methyl-1-(2-methylpropoxy)propane Chemical compound CC(C)COCC(C)C SZNYYWIUQFZLLT-UHFFFAOYSA-N 0.000 description 2
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 description 2
- MXLMTQWGSQIYOW-UHFFFAOYSA-N 3-methyl-2-butanol Chemical compound CC(C)C(C)O MXLMTQWGSQIYOW-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- 229920002126 Acrylic acid copolymer Polymers 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- FSVCELGFZIQNCK-UHFFFAOYSA-N N,N-bis(2-hydroxyethyl)glycine Chemical compound OCCN(CCO)CC(O)=O FSVCELGFZIQNCK-UHFFFAOYSA-N 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 2
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 2
- 150000008041 alkali metal carbonates Chemical class 0.000 description 2
- 125000005907 alkyl ester group Chemical group 0.000 description 2
- 150000005215 alkyl ethers Chemical class 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- 235000001014 amino acid Nutrition 0.000 description 2
- 150000001413 amino acids Chemical class 0.000 description 2
- 150000007514 bases Chemical class 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- NMJJFJNHVMGPGM-UHFFFAOYSA-N butyl formate Chemical compound CCCCOC=O NMJJFJNHVMGPGM-UHFFFAOYSA-N 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
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- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 2
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 2
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 2
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- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 description 2
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- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 150000004677 hydrates Chemical class 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
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- 150000002736 metal compounds Chemical class 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
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- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
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- 230000033116 oxidation-reduction process Effects 0.000 description 2
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 2
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- 238000003786 synthesis reaction Methods 0.000 description 2
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- 238000000108 ultra-filtration Methods 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
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- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
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- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
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Images
Description
本発明は、金属ナノ粒子の製造方法に係り、特に、マイクロリアクターを使用して高純度かつ二次粒子径が微小な金属ナノ粒子の製造方法に関する。 The present invention relates to a method for producing metal nanoparticles, and more particularly to a method for producing metal nanoparticles having a high purity and a small secondary particle diameter using a microreactor.
従来から、金属ナノ粒子は種々の用途に用いられており、例えば、スクリーン印刷、インクジェット印刷等により配線を形成するための導電性ペーストや導電性インクとして、金属ナノ粒子を媒体中に分散させた分散液が知られている。このような金属ナノ粒子分散液は、金属の酸化物や塩を反応液中で還元させることで得ることができる。
例えば、特許文献１においては、平均粒径が５０ｎｍ以下かつ耐酸化性および分散安定性に優れた銅ナノ粒子を提供する方法が開示されている。
Conventionally, metal nanoparticles have been used in various applications. For example, metal nanoparticles are dispersed in a medium as a conductive paste or conductive ink for forming wiring by screen printing, ink jet printing, or the like. Dispersions are known. Such a metal nanoparticle dispersion can be obtained by reducing a metal oxide or salt in a reaction solution.
For example, Patent Document 1 discloses a method for providing copper nanoparticles having an average particle size of 50 nm or less and excellent oxidation resistance and dispersion stability.
一方、近年、印刷性や配線の緻密性、更なる焼成温度の低下などの観点から、導電性ペーストや導電性インクに含まれる金属ナノ粒子として、金属ナノ粒子の凝集体の粒径（いわゆる、二次粒子径）が小さい分散体の製造が望まれている。
本発明者らは、特許文献１に記載の方法を参照して、金属ナノ粒子の製造を行ったところ、金属ナノ粒子の凝集体の粒径（二次粒子径）は昨今要求されるレベルより大きく、さらなる改善が必要であることを知見した。
また、各種用途への応用の点を考慮すれば、金属ナノ粒子を構成する金属原子は、実質的には１種のみの金属原子から構成されていることが好ましく、異種の金属原子がなるべく含まれないことが好ましい。つまり、金属ナノ粒子の純度がより高いことが望ましい。
On the other hand, in recent years, from the viewpoint of printability, denseness of wiring, further reduction in firing temperature, as metal nanoparticles contained in conductive paste or conductive ink, the particle size of aggregates of metal nanoparticles (so-called, Production of a dispersion having a small secondary particle size is desired.
The inventors of the present invention have produced metal nanoparticles with reference to the method described in Patent Document 1. As a result, the particle size (secondary particle size) of the aggregates of metal nanoparticles is lower than the level required recently. It was found that there was a big need for further improvement.
In consideration of application to various uses, the metal atom constituting the metal nanoparticle is preferably substantially composed of only one kind of metal atom, and includes as many different kinds of metal atoms as possible. Preferably not. That is, it is desirable that the purity of the metal nanoparticles is higher.
本発明は、上記実情に鑑みて、純度が高く、かつ、二次粒子径が小さい金属ナノ粒子を製造する方法を提供することを目的とする。 In view of the above circumstances, an object of the present invention is to provide a method for producing metal nanoparticles having high purity and small secondary particle diameter.
本発明者は、鋭意検討した結果、マイクロリアクターを用いつつ、所定の金属イオン比で金属ナノ粒子を製造することにより、上記課題を解決できることを見出した。
すなわち、以下の構成により上記目的を達成することができることを見出した。
As a result of intensive studies, the present inventor has found that the above problem can be solved by producing metal nanoparticles with a predetermined metal ion ratio while using a microreactor.
That is, it has been found that the above object can be achieved by the following configuration.
（１） マイクロリアクターを用いて、以下のＡ液およびＢ液を混合して金属ナノ粒子を製造する、金属ナノ粒子の製造方法。
Ａ液：第１の金属イオンと、第１の金属イオンの酸化還元電位よりも高い酸化還元電位を有する第２の金属イオンとを含み、第２の金属イオンの含有質量と第１の金属イオンの含有質量との比（第２の金属イオンの含有質量／第１の金属イオンの含有質量）が０．００５以下である溶液
Ｂ液：第１の金属イオンおよび第２の金属イオンを還元する還元剤を含む溶液
なお、Ａ液およびＢ液の少なくともいずれか一方には、分散剤が含まれる。
（２） 第１の金属イオンが、銅イオンである、（１）に記載の金属ナノ粒子の製造方法。
（３） 第２の金属イオンが、銀イオンおよびパラジウムイオンからなる群から選択される少なくとも１つである、（１）または（２）に記載の金属ナノ粒子の製造方法。
（４） 分散剤が、コラーゲンペプチドを含む、（１）〜（３）のいずれかに記載の金属ナノ粒子の製造方法。
（５） 金属ナノ粒子の二次粒子径が１００ｎｍ以下である、（１）〜（４）のいずれかに記載の金属ナノ粒子の製造方法。
(1) A metal nanoparticle production method for producing metal nanoparticles by mixing the following liquid A and liquid B using a microreactor.
Liquid A: containing the first metal ion and the second metal ion having a redox potential higher than the redox potential of the first metal ion, the contained mass of the second metal ion and the first metal ion Solution B solution in which the ratio to the contained mass (the contained mass of the second metal ion / the contained mass of the first metal ion) is 0.005 or less: the first metal ion and the second metal ion are reduced. Solution containing reducing agent In addition, a dispersing agent is contained in at least any one of A liquid and B liquid.
(2) The method for producing metal nanoparticles according to (1), wherein the first metal ion is a copper ion.
(3) The method for producing metal nanoparticles according to (1) or (2), wherein the second metal ion is at least one selected from the group consisting of silver ions and palladium ions.
(4) The method for producing metal nanoparticles according to any one of (1) to (3), wherein the dispersant contains a collagen peptide.
(5) The manufacturing method of the metal nanoparticle in any one of (1)-(4) whose secondary particle diameter of a metal nanoparticle is 100 nm or less.
本発明によれば、純度が高く、かつ、二次粒子径が小さい金属ナノ粒子を製造する方法を提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, the method of manufacturing a metal nanoparticle with high purity and a small secondary particle diameter can be provided.
以下に、本発明の金属ナノ粒子の製造方法の好適態様について詳述する。
まず、本発明の従来技術と比較した特徴点について詳述する。
上述したように、本発明の一つの特徴点は、酸化還元電位の異なる２種の金属イオンを含む溶液を用いて、マイクロリアクターにて金属イオンの還元を行い、金属ナノ粒子を製造している点が挙げられる。
従来のバッチ法では、溶液中における各種成分の混合がゆっくり進行するため、反応初期では十分に各成分が混合しておらず、溶液中の微小領域において各種成分の濃度のバラツキが生じやすい。そのため、反応初期で得られる金属ナノ粒子と、反応後期で得られる金属ナノ粒子とで、反応成分の濃度や分散剤の吸着量が異なり、結果として粒径のバラツキが生じてしまい、金属ナノ粒子の微粒子化が困難であった。
一方、マイクロリアクターを用いた場合は、各種成分の混合が瞬時に達成されるため、溶液中において各種成分が均一に分散する。そのため、第２の金属イオンから反応初期に形成される、触媒として機能する金属ナノ粒子がより微小かつ均一になりやすく、触媒活性を高めることができる。そのためバッチ法と比べて第２の金属イオンを減らすことができ、使用する触媒量が少なくて済むため、異種金属の量を減らすことができる。結果として、本発明においては、純度が高く、かつ、凝集が起きにくい金属ナノ粒子が得られる、と推測される。
Below, the suitable aspect of the manufacturing method of the metal nanoparticle of this invention is explained in full detail.
First, the feature point compared with the prior art of this invention is explained in full detail.
As described above, one feature of the present invention is that metal nanoparticles are produced by reducing metal ions in a microreactor using a solution containing two types of metal ions having different oxidation-reduction potentials. A point is mentioned.
In the conventional batch method, the mixing of various components in the solution proceeds slowly, so that the components are not sufficiently mixed at the initial stage of the reaction, and the concentration of the various components tends to vary in a minute region in the solution. Therefore, the metal nanoparticles obtained in the early stage of the reaction and the metal nanoparticles obtained in the late stage of the reaction differ in the concentration of the reaction components and the amount of the adsorbed dispersant, resulting in a variation in particle size, resulting in metal nanoparticles. It was difficult to make fine particles.
On the other hand, when a microreactor is used, since mixing of various components is achieved instantaneously, various components are uniformly dispersed in the solution. Therefore, the metal nanoparticles functioning as a catalyst, which are formed from the second metal ions at the initial stage of the reaction, are more likely to be minute and uniform, and the catalytic activity can be enhanced. Therefore, the second metal ion can be reduced as compared with the batch method, and the amount of the catalyst used can be reduced, so that the amount of different metals can be reduced. As a result, in the present invention, it is presumed that metal nanoparticles having high purity and less prone to aggregation can be obtained.
以下では、まず、本好適態様で使用される溶液について詳述し、その後、製造方法の手順について詳述する。 Below, the solution used by this suitable aspect is explained in full detail first, and the procedure of a manufacturing method is explained in full detail after that.
＜Ａ液＞
（金属イオン）
Ａ液は、第１の金属イオンと、第１の金属イオンの酸化還元電位よりも高い酸化還元電位を有する第２の金属イオンとを含む。Ａ液は、金属ナノ粒子を構成する金属成分を供給する役割を果たす。
なお、第２の金属イオンは、第１の金属イオンの酸化還元電位より高い酸化還元電位を示す。つまり、第２の金属イオンは、第１の金属イオンよりもより貴な金属イオンである。そのため、後述するＢ液中の還元剤との反応の際に、第２の金属イオンのほうが先に還元して、第２の金属イオン由来の金属原子を主に含む微量な金属微粒子が形成される。該金属微粒子は、第１の金属イオンの生成時の核としての機能や、第１の金属イオンの還元時の触媒としての機能を有しており、結果として得られる金属ナノ粒子がより微粒子化すると共に、二次粒子への会合が抑制される。
<Liquid A>
(Metal ions)
The liquid A includes a first metal ion and a second metal ion having a redox potential higher than the redox potential of the first metal ion. A liquid plays the role which supplies the metal component which comprises a metal nanoparticle.
The second metal ion exhibits a redox potential that is higher than the redox potential of the first metal ion. That is, the second metal ion is a more noble metal ion than the first metal ion. Therefore, during the reaction with the reducing agent in the liquid B described later, the second metal ion is reduced first, and a very small amount of metal fine particles mainly containing metal atoms derived from the second metal ion are formed. The The metal fine particles have a function as a nucleus at the time of generation of the first metal ions and a function as a catalyst at the time of reduction of the first metal ions, and the resulting metal nanoparticles are made finer. In addition, the association with secondary particles is suppressed.
第１の金属イオンの種類は特に制限されず、目的とする金属ナノ粒子の成分に合わせて適宜選択できる。例えば、第１の金属イオンとしては、銅イオンが好ましい。
上記第１の金属イオンの供給源は特に制限されず、各種金属の酢酸塩、硫酸塩、硝酸塩、炭酸塩、塩化物、臭化物、水酸化物、酸化物などの金属化合物が挙げられる。より具体的には、銅イオンを供給する場合は、例えば、水に可溶な銅の塩または水酸化物を原料として好ましく用いることができる。そのような化合物としては酢酸銅、硫酸銅、塩化銅、水酸化銅などが挙げられる。また、これらの水和物（例えば硫酸銅五水和物など）でもよい。
The type of the first metal ion is not particularly limited, and can be appropriately selected according to the target metal nanoparticle component. For example, copper ions are preferable as the first metal ions.
The supply source of the first metal ion is not particularly limited, and examples thereof include metal compounds such as acetates, sulfates, nitrates, carbonates, chlorides, bromides, hydroxides, and oxides of various metals. More specifically, when supplying copper ions, for example, a water-soluble copper salt or hydroxide can be preferably used as a raw material. Such compounds include copper acetate, copper sulfate, copper chloride, copper hydroxide and the like. These hydrates (for example, copper sulfate pentahydrate) may be used.
第２の金属イオンの種類は特に制限されず、上記第１の金属イオンの酸化還元電位と所定の関係を満たす金属イオンであればよい。例えば、第２の金属イオンとしては、金イオン、銀イオン、パラジウムイオン、白金イオン、ニッケルイオンなどが挙げられる。なかでも、銀イオンまたはパラジウムイオンが好ましい。
上記第２の金属イオンの供給源は特に制限されず、各種金属の酢酸塩、硫酸塩、硝酸塩、炭酸塩、塩化物、臭化物、水酸化物、酸化物などの金属化合物が挙げられる。
The type of the second metal ion is not particularly limited as long as it is a metal ion that satisfies a predetermined relationship with the oxidation-reduction potential of the first metal ion. For example, examples of the second metal ion include gold ion, silver ion, palladium ion, platinum ion, and nickel ion. Of these, silver ions or palladium ions are preferred.
The supply source of the second metal ion is not particularly limited, and examples thereof include metal compounds such as acetate, sulfate, nitrate, carbonate, chloride, bromide, hydroxide, and oxide of various metals.
第１の金属イオンと第２の金属イオンとの好適な組み合わせとしては、二次粒子径がより小さい金属ナノ粒子が得られる点から、第１の金属イオンが銅イオンで、第２の金属イオンが銀イオンまたはパラジウムイオンである組み合わせが挙げられる。 A preferred combination of the first metal ion and the second metal ion is that the first metal ion is a copper ion and the second metal ion because metal nanoparticles having a smaller secondary particle diameter can be obtained. Are combinations in which is a silver ion or a palladium ion.
Ａ液中における第２の金属イオンの含有質量と第１の金属イオンの含有質量との比（第２の金属イオンの含有質量／第１の金属イオンの含有質量）は、０．００５以下であり、純度がより高く、二次粒子径がより小さい金属ナノ粒子が得られる点から、０．００２以下が好ましく、０．００１以下がより好ましい。下限は特に制限されないが、触媒活性の点から、０．０００５以上が好ましい。
比が０．００５超の場合、金属ナノ粒子の純度が下がり、結果として各種用途への応用が制限される。また、第２の金属イオンは第１の金属イオンより高価であることが多く、原料コストの上昇を招く。
The ratio of the contained mass of the second metal ion and the contained mass of the first metal ion in the liquid A (the contained mass of the second metal ion / the contained mass of the first metal ion) is 0.005 or less. In view of obtaining metal nanoparticles having higher purity and smaller secondary particle diameter, 0.002 or less is preferable, and 0.001 or less is more preferable. Although a minimum in particular is not restrict | limited, 0.0005 or more is preferable from the point of catalyst activity.
When the ratio is more than 0.005, the purity of the metal nanoparticles is lowered, and as a result, application to various uses is limited. In addition, the second metal ion is often more expensive than the first metal ion, leading to an increase in raw material cost.
Ａ液中における第１の金属イオンおよび第２の金属イオンの合計モル濃度は特に制限されないが、取扱い性に優れ、二次粒子径がより小さい金属ナノ粒子が得られる点で、０．００１〜５．０モル／ｌが好ましく、０．０１〜２．０モル／ｌがより好ましい。 The total molar concentration of the first metal ion and the second metal ion in the liquid A is not particularly limited. However, 0.001 to 0.001 in that metal nanoparticles having excellent handleability and a smaller secondary particle diameter can be obtained. 5.0 mol / l is preferable, and 0.01 to 2.0 mol / l is more preferable.
（その他成分）
Ａ液には、必要に応じて、上記金属イオン以外の成分が含まれていてもよい。以下、各種任意成分について詳述する。
(Other ingredients)
The A liquid may contain components other than the above metal ions as necessary. Hereinafter, various optional components will be described in detail.
（溶媒）
通常、Ａ液には、溶媒が含まれる。溶媒としては、例えば、水、アルコール類、エーテル類、エステル類などの有機溶媒を幅広く用いることが可能であり、特に限定されないが、分散安定性の観点から、水、１〜３価のヒドロキシル基を有する脂肪族アルコール、アルコール由来のアルキルエーテル、および、アルコール由来のアルキルエステルからなる群から選択される少なくとも１種が好ましく用いられる。
(solvent)
Usually, the A liquid contains a solvent. As the solvent, for example, organic solvents such as water, alcohols, ethers and esters can be widely used, and are not particularly limited. However, from the viewpoint of dispersion stability, water, 1 to 3 valent hydroxyl groups are used. Preferably, at least one selected from the group consisting of an aliphatic alcohol having an alcohol, an alkyl ether derived from alcohol, and an alkyl ester derived from alcohol is preferably used.
溶媒として、水を用いる場合には、イオン交換水等のレベルの純度を有するものが好ましい。 When water is used as the solvent, a solvent having a level of purity such as ion-exchanged water is preferable.
１〜３価のヒドロキシル基を有する脂肪族アルコールとしては、メタノール、エタノール、１−プロパノール、１−ブタノール、１−ペンタノール、１−ヘキサノール、シクロヘキサノール、１−ヘプタノール、１−オクタノール、１−ノナノール、１−デカノール、グリシドール、メチルシクロヘキサノール、２−メチル１−ブタノール、３−メチル−２−ブタノール、４−メチル−２−ペンタノール、イソプロピルアルコール、２−エチルブタノール、２−エチルヘキサノール、２−オクタノール、テルピネオール、ジヒドロテルピネオール、２−メトキシエタノール、２−エトキシエタノール、２−ｎ−ブトキシエタノール、２−フェノキシエタノール、カルビトール、エチルカルビトール、ｎ−ブチルカルビトール、ジアセトンアルコール、エチレングリコール、ジエチレングリコールトリエチレングリコール、テトラエチレングリコール、プロピレングリコール、トリメチレングリコール、ジプロピレングリコール、トリプロピレングリコール、１，２−ブチレングリコール、１，３−ブチレングリコール、１，４−ブチレングリコール、ペンタメチレングリコール、へキシレングリコール、グリセリンなどが挙げられる。
なかでも、１〜３価のヒドロキシル基を有する炭素数１〜４の脂肪族アルコールが、沸点が高すぎず焼結後に残存しにくいことからより好ましく、具体的には、メタノール、エチレングリコール、グリセリン、２−メトキシエタノール、ジエチレングリコールであることが好ましい。
Examples of aliphatic alcohols having 1 to 3 hydroxyl groups include methanol, ethanol, 1-propanol, 1-butanol, 1-pentanol, 1-hexanol, cyclohexanol, 1-heptanol, 1-octanol and 1-nonanol. 1-decanol, glycidol, methylcyclohexanol, 2-methyl 1-butanol, 3-methyl-2-butanol, 4-methyl-2-pentanol, isopropyl alcohol, 2-ethylbutanol, 2-ethylhexanol, 2- Octanol, terpineol, dihydroterpineol, 2-methoxyethanol, 2-ethoxyethanol, 2-n-butoxyethanol, 2-phenoxyethanol, carbitol, ethyl carbitol, n-butyl carbitol, diacetone alcohol , Ethylene glycol, diethylene glycol triethylene glycol, tetraethylene glycol, propylene glycol, trimethylene glycol, dipropylene glycol, tripropylene glycol, 1,2-butylene glycol, 1,3-butylene glycol, 1,4-butylene glycol , Pentamethylene glycol, hexylene glycol, glycerin and the like.
Among these, aliphatic alcohols having 1 to 3 carbon atoms and having 1 to 3 hydroxyl groups are more preferable because the boiling point is not too high and hardly remains after sintering. Specifically, methanol, ethylene glycol, glycerin 2-methoxyethanol and diethylene glycol are preferred.
エーテル類としては、上記アルコール由来のアルキルエーテルが挙げられ、ジエチルエーテル、ジイソブチルエーテル、ジブチルエーテル、メチル−ｔ−ブチルエーテル、メチルシクロヘキシルエーテル、ジエチレングリコールジメチルエーテル、ジエチレングリコールジエチルエーテル、トリエチレングリコールジメチルエーテル、トリエチレングリコールジエチルエーテル、テトラヒドロフラン、テトラヒドロピラン、１，４−ジオキサンなどが例示される。
なかでも、１〜３価のヒドロキシル基を有する炭素数１〜４の脂肪族アルコール由来の炭素数２〜８のアルキルエーテルが好ましく、具体的には、ジエチルエーテル、ジエチレングリコールジメチルエーテル、テトラヒドロフランがより好ましい。
Examples of ethers include alkyl ethers derived from the above alcohols, such as diethyl ether, diisobutyl ether, dibutyl ether, methyl-t-butyl ether, methyl cyclohexyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl. Examples include ether, tetrahydrofuran, tetrahydropyran, 1,4-dioxane and the like.
Especially, the C2-C8 alkyl ether derived from a C1-C4 aliphatic alcohol which has a 1-3 valent hydroxyl group is preferable, and specifically, diethyl ether, diethylene glycol dimethyl ether, and tetrahydrofuran are more preferable.
エステル類としては、上記アルコール由来のアルキルエステルが挙げられ、ギ酸メチル、ギ酸エチル、ギ酸ブチル、酢酸メチル、酢酸エチル、酢酸ブチル、プロピオン酸メチル、プロピオン酸エチル、プロピオン酸ブチル、γ−ブチロラクトンなどが例示される。
なかでも、１〜３価のヒドロキシル基を有する炭素数１〜４の脂肪族アルコール由来の炭素数２〜８のアルキルエステルが好ましく、具体的には、ギ酸メチル、ギ酸エチル、酢酸メチルがより好ましい。
Examples of the esters include alkyl esters derived from the above alcohols, such as methyl formate, ethyl formate, butyl formate, methyl acetate, ethyl acetate, butyl acetate, methyl propionate, ethyl propionate, butyl propionate, and γ-butyrolactone. Illustrated.
Especially, the C2-C8 alkyl ester derived from a C1-C4 aliphatic alcohol which has a 1-3 valent hydroxyl group is preferable, Specifically, methyl formate, ethyl formate, and methyl acetate are more preferable. .
上記溶媒の中でも、沸点が高すぎないことから、特に水を主溶媒として用いることが好ましい。主溶媒とは、溶媒の中で含有率が最も多い溶媒である。 Among these solvents, it is particularly preferable to use water as the main solvent because the boiling point is not too high. The main solvent is a solvent having the highest content in the solvent.
（分散剤）
Ａ液および後述するＢ液の少なくともいずれか一方には、金属ナノ粒子を分散安定化させる分散剤が含まれる。分散剤は、金属ナノ粒子の表面に吸着し、金属ナノ粒子同士の凝集を抑制し、分散安定性を向上させる保護剤として機能する。
使用される分散剤の種類は特に制限されず、公知の分散剤を使用することができる。例えば、アルキルアミン、アルカンチオール、アルカンジオールなどの低分子型分散剤や、各種官能基を有する高分子型分散剤などが挙げられる。
なお、高分子型分散剤としては、例えば、スチレン系樹脂（スチレン−（メタ）アクリル酸共重合体、スチレン−無水マレイン酸共重合体など）、アクリル系樹脂（（メタ）アクリル酸メチル−（メタ）アクリル酸共重合体、ポリ（メタ）アクリル酸などの（メタ）アクリル酸系樹脂など）、水溶性ウレタン樹脂、水溶性アクリルウレタン樹脂、水溶性エポキシ樹脂、水溶性ポリエステル系樹脂、セルロース誘導体（ニトロセルロース；エチルセルロースなどのアルキルセルロース、エチルヒドロキシエチルセルロースなどのアルキル−ヒドロキシアルキルセルロース、ヒドロキシエチルセルロース、ヒドロキシプロピルセルロースなどのヒドロキシアルキルセルロース、カルボキシメチルセルロースなどのカルボキシアルキルセルロースなどのセルロースエーテル類など）、ポリビニルアルコール、ポリアルキレングリコール（液状のポリエチレングリコール、ポリプロピレングリコールなど）、天然高分子（ゼラチン、デキストリン、アラビヤゴム、カゼインなどの多糖類など）、ポリエチレンスルホン酸またはその塩、ポリスチレンスルホン酸またはその塩、ナフタレンスルホン酸のホルマリン縮合物、窒素原子含有高分子化合物［例えば、ポリアルキレンイミン（ポリエチレンイミンなど）、ポリビニルピロリドン、ポリアリルアミン、ポリエーテルポリアミン（ポリオキシエチレンポリアミンなど）などのアミノ基を有する高分子化合物］などが挙げられる。
(Dispersant)
At least one of the liquid A and the liquid B described later contains a dispersant for dispersing and stabilizing the metal nanoparticles. The dispersant functions as a protective agent that adsorbs to the surface of the metal nanoparticles, suppresses aggregation of the metal nanoparticles, and improves dispersion stability.
The kind in particular of dispersing agent to be used is not restrict | limited, A well-known dispersing agent can be used. Examples thereof include low molecular weight dispersants such as alkylamines, alkanethiols, and alkanediols, and polymer type dispersants having various functional groups.
Examples of the polymer dispersant include styrene resin (styrene- (meth) acrylic acid copolymer, styrene-maleic anhydride copolymer, etc.), acrylic resin (methyl (meth) acrylate- ( (Meth) acrylic acid copolymers, (meth) acrylic resins such as poly (meth) acrylic acid), water-soluble urethane resins, water-soluble acrylic urethane resins, water-soluble epoxy resins, water-soluble polyester resins, cellulose derivatives (Nitrocellulose; alkyl cellulose such as ethyl cellulose; alkyl-hydroxyalkyl cellulose such as ethyl hydroxyethyl cellulose; hydroxyalkyl cellulose such as hydroxyethyl cellulose and hydroxypropyl cellulose; carboxyalkyl cellulose such as carboxymethyl cellulose; Cellulose ethers), polyvinyl alcohol, polyalkylene glycol (liquid polyethylene glycol, polypropylene glycol, etc.), natural polymers (polysaccharides such as gelatin, dextrin, arabic gum, casein), polyethylene sulfonic acid or salts thereof, polystyrene Sulfonic acid or its salt, formalin condensate of naphthalenesulfonic acid, nitrogen atom-containing polymer compound [for example, polyalkyleneimine (polyethyleneimine etc.), polyvinylpyrrolidone, polyallylamine, polyether polyamine (polyoxyethylene polyamine etc.) Polymer compound having an amino group] and the like.
分散剤のなかでも、得られる金属ナノ粒子の二次粒子径をより小さくでき、金属ナノ粒子の分散安定性および耐酸化性により優れる点で、重量平均分子量１００００以下のコラーゲンペプチドが好ましい。
金属ナノ粒子表面における密度を高くして耐酸化性を向上させるという理由から、コラーゲンペプチドの重量平均分子量は７０００以下であることが好ましく、６８００以下であることがより好ましく、５０００以下であることがさらに好ましく、３０００以下であることが特に好ましい。また、金属ナノ粒子との吸着点を多くすることで金属ナノ粒子から遊離しにくい状態で被覆し、分散安定性を向上させるという理由から、コラーゲンペプチドの重量平均分子量は１０００以上であることが好ましく、２０００以上であることがより好ましく、２７００以上であることがさらに好ましい。
コラーゲンペプチドの重量平均分子量は、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）を用いて確認できる。即ち、ＧＰＣでコラーゲンペプチドの重量平均分子量を求めるには、あらかじめ分子量が既知でそれぞれ異なる複数のポリマー（例えばポリエチレングリコール：ＰＥＧ）数種を同条件で測定して得られたリテンションタイムと分子量との関係の検量線を元に算出すればよい。本発明における平均分子量とは、この手法に従ってＧＰＣより算出した重量平均分子量を指す。
Among the dispersants, a collagen peptide having a weight average molecular weight of 10,000 or less is preferable because the secondary particle diameter of the obtained metal nanoparticles can be further reduced and the dispersion stability and oxidation resistance of the metal nanoparticles are excellent.
The weight average molecular weight of the collagen peptide is preferably 7000 or less, more preferably 6800 or less, and more preferably 5000 or less because the density on the metal nanoparticle surface is increased to improve oxidation resistance. More preferred is 3000 or less. In addition, it is preferable that the weight average molecular weight of the collagen peptide is 1000 or more because it is difficult to release from the metal nanoparticles by increasing the number of adsorption points with the metal nanoparticles and the dispersion stability is improved. , More preferably 2000 or more, and further preferably 2700 or more.
The weight average molecular weight of the collagen peptide can be confirmed using gel permeation chromatography (GPC). That is, in order to determine the weight average molecular weight of a collagen peptide by GPC, the retention time and molecular weight obtained by measuring several types of polymers (for example, polyethylene glycol: PEG) having different molecular weights that are different from each other under the same conditions. What is necessary is just to calculate based on the calibration curve of a relationship. The average molecular weight in the present invention refers to a weight average molecular weight calculated from GPC according to this method.
コラーゲンペプチドは、ゼラチンを酵素や酸、アルカリなどで加水分解して得られたものであり、グリシンを多く含むタンパク質であり、市販品としても入手可能である。ゼラチンを加水分解する方法には特に制限がなく、従来公知の方法を用いて行うことができる。
また、コラーゲンペプチドを構成するアミノ酸組成およびアミノ酸数については、上記分子量の範囲内であれば特に制限はなく、例えば、アミノ酸を３残基（ペプチド結合２個）有するコラーゲントリペプチドなど、ペプチド結合を２〜６個有するオリゴペプチドが挙げられる。
本発明におけるコラーゲンペプチドとして市販品を用いる場合、ナチコール１０００（ＷＥＩＳＨＡＲＤＴ製、重量平均分子量２７００）、ナチコール４０００（ＷＥＩＳＨＡＲＤＴ製、重量平均分子量６８００）などを用いることができる。
Collagen peptide is obtained by hydrolyzing gelatin with an enzyme, acid, alkali or the like, is a protein containing a large amount of glycine, and is also available as a commercial product. There is no restriction | limiting in particular in the method of hydrolyzing gelatin, It can carry out using a conventionally well-known method.
The amino acid composition and the number of amino acids constituting the collagen peptide are not particularly limited as long as they are within the above molecular weight range. For example, a peptide bond such as a collagen tripeptide having 3 amino acid residues (2 peptide bonds) is used. An oligopeptide having 2 to 6 is exemplified.
When a commercially available product is used as the collagen peptide in the present invention, Nachicol 1000 (manufactured by WEISHARDT, weight average molecular weight 2700), Nachicol 4000 (manufactured by WEISHARDT, weight average molecular weight 6800) and the like can be used.
分散剤の使用量は特に制限されず、二次粒子径がより小さい金属ナノ粒子が得られる点で、上述した第１の金属イオンおよび第２の金属イオンの合計質量１００質量部に対して、１０〜３０００質量部が好ましく、２０〜１００質量部がより好ましい。 The amount of the dispersant to be used is not particularly limited, and in terms of obtaining metal nanoparticles having a smaller secondary particle diameter, the total mass of the first metal ion and the second metal ion described above is 100 parts by mass. 10-3000 mass parts is preferable, and 20-100 mass parts is more preferable.
（錯化剤）
Ａ液には、必要に応じて、錯化剤が含まれる。錯化剤を使用することにより、上述した第１の金属イオンおよび第２の金属イオンの溶媒に対する溶解性を向上させることができる。
錯化剤としては、金属イオンと錯体を形成するものであれば限定されないが、酸素原子、窒素原子、または、硫黄原子を含む配位性の官能基を有するものが好ましい。そのような官能基としては、水酸基、カルボキシル基、カルボニル基、アミド基、アミノ基、チオール基などが挙げられ、水酸基、カルボキシル基、アミド基、アミノ基が好ましい。また、これら官能基を、同一分子内に二種類以上含有する形態も好ましい。
錯化剤としては、例えば、乳酸、リンゴ酸、酒石酸、クエン酸、グルコン酸などのオキシカルボン酸またはこれらの塩、ニトリロ三酢酸、エチレンジアミン四酢酸（ＥＤＴＡ）、ヒドロキシエチルエチレンジアミン三酢酸、ジエチレントリアミン五酢酸、トリエチレンテトラミン六酢酸、１，３−プロパンジアミン四酢酸、ヒドロキシエチルイミノ二酢酸、Ｎ，Ｎ−ジ（２−ヒドロキシエチル）グリシン（ＤＨＥＧ）、グリコールエーテルジアミン四酢酸、アスパラギン酸二酢酸、メチルグリシン二酢酸、グルタミン酸二酢酸、エチレンジアミンジコハク酸などのアミノカルボン酸またはこれらの塩、トリエタノールアミン、グリセリンが挙げられ、酒石酸、Ｎ，Ｎ−ジ（２−ヒドロキシエチル）グリシン（ＤＨＥＧ）が好ましい。また、これらの塩（例えば酒石酸ナトリウムなど）でもよく、水和物（例えば酒石酸ナトリウム二水和物など）でもよい。
(Complexing agent)
The A liquid contains a complexing agent as necessary. By using the complexing agent, the solubility of the first metal ion and the second metal ion described above in the solvent can be improved.
The complexing agent is not limited as long as it forms a complex with a metal ion, but those having a coordinating functional group containing an oxygen atom, a nitrogen atom, or a sulfur atom are preferable. Examples of such a functional group include a hydroxyl group, a carboxyl group, a carbonyl group, an amide group, an amino group, and a thiol group, and a hydroxyl group, a carboxyl group, an amide group, and an amino group are preferable. Moreover, the form which contains two or more types of these functional groups in the same molecule is also preferable.
Examples of complexing agents include oxycarboxylic acids such as lactic acid, malic acid, tartaric acid, citric acid, and gluconic acid or salts thereof, nitrilotriacetic acid, ethylenediaminetetraacetic acid (EDTA), hydroxyethylethylenediaminetriacetic acid, diethylenetriaminepentaacetic acid. , Triethylenetetramine hexaacetic acid, 1,3-propanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, N, N-di (2-hydroxyethyl) glycine (DHEG), glycol etherdiaminetetraacetic acid, aspartic acid diacetic acid, methyl Examples thereof include aminocarboxylic acids such as glycine diacetic acid, glutamic acid diacetic acid, ethylenediamine disuccinic acid or salts thereof, triethanolamine, and glycerin, and tartaric acid and N, N-di (2-hydroxyethyl) glycine (DHEG) are preferable. . Moreover, these salts (for example, sodium tartrate etc.) may be sufficient, and hydrates (for example, sodium tartrate dihydrate etc.) may be sufficient.
錯化剤の使用量は特に制限されず、二次粒子径がより小さい金属ナノ粒子が得られる点で、上述した第１の金属イオンおよび第２の金属イオンの合計モル量に対して、５０〜４００モル％が好ましく、１００〜２００モル％がより好ましい。 The amount of the complexing agent used is not particularly limited, and is 50% relative to the total molar amount of the first metal ion and the second metal ion described above in that metal nanoparticles having a smaller secondary particle diameter can be obtained. -400 mol% is preferable and 100-200 mol% is more preferable.
（ｐＨ調整剤）
Ａ液には、必要に応じて、Ａ液のｐＨを調整するためのｐＨ調整剤が含まれていてもよい。
ｐＨ調整剤としては、公知の酸性化合物や塩基性化合物を使用できる。
酸性化合物としては、例えば、塩酸、硫酸、硫酸などを使用できる。塩基性化合物としては、例えば、水溶性アルカリ金属化合物（アルカリ金属水酸化物、アルカリ金属炭酸塩、アルカリ金属炭酸水酸化物）、アンモニア、アンモニウム塩化合物などが挙げられる。
(PH adjuster)
The A liquid may contain a pH adjuster for adjusting the pH of the A liquid as necessary.
As the pH adjuster, known acidic compounds and basic compounds can be used.
As the acidic compound, for example, hydrochloric acid, sulfuric acid, sulfuric acid and the like can be used. Examples of the basic compound include water-soluble alkali metal compounds (alkali metal hydroxide, alkali metal carbonate, alkali metal carbonate hydroxide), ammonia, ammonium salt compounds, and the like.
＜Ｂ液＞
Ｂ液には、上述した第１の金属イオンおよび第２の金属イオンを還元する還元剤が含まれる。該還元剤により、第１の金属イオンおよび第２の金属イオンはそれぞれ金属原子に還元される。
還元剤としては、上記第１の金属イオンおよび第２の金属イオンを金属原子に還元することができれば、その種類は特に制限されず、公知の還元剤を使用することができる。例えば、ヒドラジン、塩酸ヒドラジン、硫酸ヒドラジン、抱水ヒドラジンなどのヒドラジン系還元剤や、水素化ホウ素ナトリウム、亜硫酸ナトリウム、亜硫酸水素ナトリウム、チオ硫酸ナトリウム、亜硝酸ナトリウム、次亜硝酸ナトリウム、亜リン酸、亜リン酸ナトリウム、次亜リン酸、次亜リン酸ナトリウム、アルデヒド類、アルコール類、アミン類、糖類などが挙げられ、これらを１種または２種以上を用いてもよい。
<Liquid B>
The B liquid contains a reducing agent that reduces the first metal ion and the second metal ion described above. By the reducing agent, the first metal ion and the second metal ion are reduced to metal atoms, respectively.
The reducing agent is not particularly limited as long as the first metal ion and the second metal ion can be reduced to metal atoms, and a known reducing agent can be used. For example, hydrazine reducing agents such as hydrazine, hydrazine hydrochloride, hydrazine sulfate, hydrazine hydrate, sodium borohydride, sodium sulfite, sodium bisulfite, sodium thiosulfate, sodium nitrite, sodium hyponitrite, phosphorous acid, Examples thereof include sodium phosphite, hypophosphorous acid, sodium hypophosphite, aldehydes, alcohols, amines, saccharides and the like, and these may be used alone or in combination.
還元剤の使用量は特に制限されず、還元を完全に完結させる点と二次粒子径がより小さい金属ナノ粒子が得られる点で、上述した第１の金属イオンおよび第２の金属イオンの合計モル量に対して、１００〜８００モル％であることが好ましく、１５０〜４００モル％であることがより好ましい。 The amount of the reducing agent used is not particularly limited, and is the sum of the first metal ion and the second metal ion described above in that the reduction is completely completed and metal nanoparticles having a smaller secondary particle diameter are obtained. The molar amount is preferably 100 to 800 mol%, and more preferably 150 to 400 mol%.
Ｂ液中における還元剤の濃度は特に制限されないが、取扱い性に優れ、二次粒子径がより小さい金属ナノ粒子が得られる点で、Ｂ液全量に対して、０．００１〜５．０モル／ｌが好ましく、０．０１〜２．０モル／ｌがより好ましい。 The concentration of the reducing agent in the B liquid is not particularly limited, but 0.001 to 5.0 moles with respect to the total amount of the B liquid in that metal nanoparticles having a small secondary particle diameter are obtained with excellent handleability. / L is preferable, and 0.01 to 2.0 mol / l is more preferable.
Ｂ液には、上記還元剤以外の他の成分が含まれていてもよい。例えば、上述した溶媒、保護剤、ｐＨ調整剤などが挙げられる。 The B liquid may contain components other than the reducing agent. For example, the solvent mentioned above, a protective agent, a pH adjuster etc. are mentioned.
＜製造方法の手順＞
本発明の金属ナノ粒子の製造方法は、マイクロリアクターを用いて、上述したＡ液およびＢ液を混合して、金属ナノ粒子を製造する方法である。
以下では、本方法で使用されるマイクロリアクター、および、混合条件について詳述する。
<Procedure of manufacturing method>
The method for producing metal nanoparticles of the present invention is a method for producing metal nanoparticles by mixing the liquid A and the liquid B described above using a microreactor.
Below, the microreactor used by this method and mixing conditions are explained in full detail.
（マイクロリアクター）
マイクロリアクターとは、複数の物質を混合する混合部（マイクロミキサー）とそれに続く所望の反応を生じさせる流路（反応部）からなる微小流通式反応器であり、混合部および反応部の流路断面の最小長さが数μｍから数千μｍのものが代表的である。マイクロミキサーには、通常、複数の流入路が連通しており、該流入路を通じて供給される複数の液体（原料化合物）は、混合部（マイクロミキサー）で合流することにより、混合され、それに続く流路（反応部）にて所定の反応が生じる。
混合部（マイクロミキサー）の形状等については特に制限はなく、Ｔ字型ミキサーやＹ字型ミキサー等の公知のものを使用できる。
混合部（マイクロミキサー）に繋がる流入路の口径は特に制限されないが、０．０１〜１０００μｍ程度が好ましい。
また、流路（反応部）の口径は特に制限されないが、１μｍ〜１０ｍｍ程度が好ましく、拡散混合を進める点で１〜１００μｍがより好ましい。
(Microreactor)
A microreactor is a micro flow reactor comprising a mixing section (micromixer) for mixing a plurality of substances and a flow path (reaction section) for causing a desired reaction, and a flow path for the mixing section and the reaction section. Typically, the minimum cross-sectional length is from several μm to several thousand μm. In general, a plurality of inflow passages communicate with the micromixer, and a plurality of liquids (raw material compounds) supplied through the inflow passage are mixed together by a mixing section (micromixer), followed by the mixture. A predetermined reaction occurs in the flow path (reaction part).
There is no restriction | limiting in particular about the shape of a mixing part (micro mixer), Well-known things, such as a T-shaped mixer and a Y-shaped mixer, can be used.
The diameter of the inflow path connected to the mixing part (micromixer) is not particularly limited, but is preferably about 0.01 to 1000 μm.
The diameter of the flow path (reaction part) is not particularly limited, but is preferably about 1 μm to 10 mm, and more preferably 1 to 100 μm from the viewpoint of promoting diffusion mixing.
本発明においては、上述したＡ液およびＢ液を混合することができれば使用されるマイクロリアクターの種類は特に制限されず、公知のマイクロリアクターを使用することができる。
市販されているマイクロリアクターとしては、例えば、インターディジタルチャンネル構造体を備えるマイクロリアクター、インスティチュート・フュール・マイクロテクニック・マインツ（ＩＭＭ）社製シングルミキサーおよびキャタピラーミキサー；ミクログラス社製ミクログラスリアクター；ＣＰＣシステムス社製サイトス；山武社製ＹＭ−１、ＹＭ−２型ミキサー；島津ＧＬＣ社製ミキシングティーおよびティー（Ｔ字型コネクタ、Ｙ字型コネクタ）；マイクロ化学技研社製ＩＭＴチップリアクター；東レエンジニアリング開発品マイクロ・ハイ・ミキサー；中心衝突型ミキサー（Ｋ−Ｍ型）等が挙げられ、いずれも本発明に使用することができる。
In the present invention, the type of microreactor used is not particularly limited as long as the above-described A liquid and B liquid can be mixed, and a known microreactor can be used.
Commercially available microreactors include, for example, a microreactor having an interdigital channel structure, a single mixer and a caterpillar mixer manufactured by Institute Full Microtechnique Mainz (IMM); a microglass reactor manufactured by Microglass; CPC Systems'Cytos; Yamatake YM-1, YM-2 type mixer; Shimadzu GLC's mixing tee and tee (T-shaped connector, Y-shaped connector); Micro Chemical Giken IMT chip reactor; Toray Engineering-developed micro-high mixer; center collision type mixer (KM type) and the like can be mentioned, and any of them can be used in the present invention.
図１に、本発明で使用されるマイクロリアクターの一概略図を示す。
図１に示すマイクロリアクター（ＭＲ）は、マイクロミキサー（Ｍ）とマイクロチューブ（Ｒ）とで構成される。マイクロリアクター（ＭＲ）には２つの原料供給口（点１，点２）と、１つの生成物出口（点６）があり、原料供給口の一方にはＡ液を供給し、もう一方の供給口にはＢ液を供給する。溶液Ａおよび溶液ＢはマイクロミキサーＭの点５で接触し混合し、点５から点６の区間で反応が完了し、生成物が得られる。
なお、点１，２はマイクロリアクターへの原料供給口、点３，４はマイクロミキサーへの原料供給口、点はＡ液とＢ液の混合開始点、点６はリアクターの出口を示す。
FIG. 1 shows a schematic diagram of a microreactor used in the present invention.
The microreactor (MR) shown in FIG. 1 includes a micromixer (M) and a microtube (R). The microreactor (MR) has two raw material supply ports (points 1 and 2) and one product outlet (point 6). The liquid A is supplied to one of the raw material supply ports, and the other supply B liquid is supplied to the mouth. Solution A and solution B are contacted and mixed at
The
マイクロリアクターに供給されるＡ液およびＢ液の流速は、マイクロミキサーの混合方式、構造、および流路の直径によって好ましい流速は異なる。また、Ａ液およびＢ液のマイクロリアクターに供給される流速は、各々が同じ流量であっても異なる流量であってもよい。
マイクロリアクターにおけるレイノルズ数は特に制限されないが、二次粒子径がより小さい金属粒子が得られる点で、１００〜３０００に制御することが好ましい。なお、レイノルズ数とは下記の式（１）に従って計算されるものである。
式（１） レイノルズ数Ｒｅ＝Ｄ＜υx＞ρ／μ
Ｄは流路の等価直径、＜υx＞は断面平均速度、ρは流体の密度、μは流体の粘度を表す。
さらに、送液用のポンプは工業的に使用される送液ポンプのいずれでも使用可能だが、できるだけ送液時に脈動を生じない機種が望ましい。好ましくは、プランジャーポンプ、ギアーポンプ、ロータリーポンプ、ダイヤフラムポンプなどである。
The preferred flow rates of the liquids A and B supplied to the microreactor vary depending on the mixing method, structure, and diameter of the flow channel of the micromixer. Further, the flow rates supplied to the liquid A and B liquid microreactors may be the same or different.
The Reynolds number in the microreactor is not particularly limited, but is preferably controlled to 100 to 3000 in that metal particles having a smaller secondary particle diameter can be obtained. The Reynolds number is calculated according to the following equation (1).
Formula (1) Reynolds number Re = D <υx> ρ / μ
D is the equivalent diameter of the flow path, <υx> is the average cross-sectional velocity, ρ is the density of the fluid, and μ is the viscosity of the fluid.
Furthermore, although the pump for liquid feeding can be used with any of the liquid feeding pumps used industrially, a model that does not cause pulsation at the time of liquid feeding is desirable. A plunger pump, a gear pump, a rotary pump, a diaphragm pump, and the like are preferable.
本発明で用いられるマイクロリアクターでは冷却や加熱が可能であるが、温度調節方法は特に限定されない。反応温度制御は、例えば、マイクロリアクターの流路壁面から熱媒体との熱交換により行なわれるが、マイクロリアクターに導入するＡ液およびＢ液をあらかじめ熱交換器により所望の温度に調製したものを供給してもよい。
なお、Ａ液およびＢ液を混合する際の温度条件は特に制限されないが、二次粒子径のより小さい金属ナノ粒子が得られる点で、１０〜９０℃が好ましく、４０〜８０℃がより好ましい。
The microreactor used in the present invention can be cooled or heated, but the temperature control method is not particularly limited. The reaction temperature control is performed, for example, by heat exchange with the heat medium from the channel wall surface of the microreactor. Supply liquids A and B introduced into the microreactor in advance to a desired temperature with a heat exchanger. May be.
In addition, although the temperature conditions at the time of mixing A liquid and B liquid are not restrict | limited, 10-90 degreeC is preferable and 40-80 degreeC is more preferable at the point from which the metal nanoparticle with a smaller secondary particle diameter is obtained. .
本発明における反応時間は、Ａ液およびＢ液がマイクロミキサー入り口に導入され、マイクロミキサー出口に接続された反応部を通って出口から外へ出るまでの滞留時間で表わされる。滞留時間は、使用するマイクロリアクターの内部空間容積に応じてＡ液およびＢ液の供給速度を変更することで設定を行うが、Ａ液およびＢ液の供給時間が決まっている場合にはマイクロリアクターの内部空間容積を変更することで設定してもよく、マイクロチューブの断面積および長さを調節することにより設定してもよい。
滞留時間としては、二次粒子径がより小さい金属ナノ粒子が得られる点で、０．１〜１００秒が好ましく、０．１〜１０秒がより好ましい。
The reaction time in the present invention is represented by the residence time from when the liquid A and the liquid B are introduced into the micromixer inlet to the outside through the reaction section connected to the micromixer outlet. The residence time is set by changing the supply speed of liquid A and liquid B according to the internal space volume of the microreactor to be used. When the supply time of liquid A and liquid B is determined, the microreactor It may be set by changing the internal space volume of the tube or by adjusting the cross-sectional area and length of the microtube.
The residence time is preferably from 0.1 to 100 seconds, more preferably from 0.1 to 10 seconds, in that metal nanoparticles having a smaller secondary particle diameter can be obtained.
なお、混合部、反応部および流入路などの材質は、耐熱、耐圧および耐溶剤性、加工容易性等の要求に応じて、ステンレス鋼、チタン、銅、ニッケル、アルミニウムなどの金属、ガラス、フォチュランガラス、各種セラミックス、ピーク樹脂、ポリイミド樹脂、縁プラプラスチック、シリコン、および、ＰＦＡ、ＴＦＡＡなどのテフロン（登録商標）樹脂等を好適に使用できる。 The materials for the mixing section, reaction section, and inflow path can be selected from metals such as stainless steel, titanium, copper, nickel, and aluminum, glass, foam, etc. according to requirements such as heat resistance, pressure resistance and solvent resistance, and processability. Chulan glass, various ceramics, peak resin, polyimide resin, plastic edge plastic, silicon, and Teflon (registered trademark) resin such as PFA and TFAA can be suitably used.
＜金属ナノ粒子＞
上記手順により得られる金属ナノ粒子は、純度が高く、二次粒子径も小さい。なお、通常、Ａ液およびＢ液には溶媒が含まれるため、上記手順を経て金属ナノ粒子が溶媒中に分散した分散液（金属ナノ粒子分散液）として得られる。
得られる金属ナノ粒子の純度としては、９９．５％以上が好ましく、９９．８％以上がより好ましい。なお、ここで純度とは、上記方法で得られる金属ナノ粒子の全金属原子に対する、主成分として含まれる第１の金属イオン由来の金属原子の質量割合を意図する。
<Metal nanoparticles>
The metal nanoparticles obtained by the above procedure have a high purity and a small secondary particle size. In addition, since a solvent is normally contained in A liquid and B liquid, it obtains as a dispersion liquid (metal nanoparticle dispersion liquid) which the metal nanoparticle disperse | distributed in the solvent through the said procedure.
The purity of the metal nanoparticles obtained is preferably 99.5% or more, more preferably 99.8% or more. Here, purity means the mass ratio of metal atoms derived from the first metal ion contained as the main component with respect to all metal atoms of the metal nanoparticles obtained by the above method.
また、得られる金属ナノ粒子の二次粒子径（金属ナノ粒子の凝集体の粒径）は特に制限されないが、導電ペーストなどの用途への応用の点からは、１００ｎｍ以下が好ましく、８０ｎｍ以下がより好ましい。下限は特に制限されないが、通常、金属ナノ粒子の一次粒子径である。
なお、金属ナノ粒子の二次粒子径とは平均二次粒子径のことを意図し、金属ナノ粒子分散液中に存在する、連結していない一次粒子を含む全ての金属ナノ粒子の平均粒子径を指す。二次粒子径は、得られた金属ナノ粒子分散液を用いて、動的光散乱法（例えば、Marveln社製動的光散乱測定装置（ゼータサイザーＺＳ））により数平均粒子径を測定して求められる。
Further, the secondary particle diameter of the metal nanoparticles obtained (the particle diameter of the aggregates of metal nanoparticles) is not particularly limited, but is preferably 100 nm or less, and preferably 80 nm or less from the viewpoint of application to conductive pastes and the like. More preferred. Although a minimum in particular is not restrict | limited, Usually, it is a primary particle diameter of a metal nanoparticle.
In addition, the secondary particle diameter of the metal nanoparticles is intended to mean the average secondary particle diameter, and the average particle diameter of all the metal nanoparticles including unconnected primary particles present in the metal nanoparticle dispersion liquid. Point to. The secondary particle size is obtained by measuring the number average particle size by the dynamic light scattering method (for example, dynamic light scattering measuring device (Zetasizer ZS) manufactured by Marveln) using the obtained metal nanoparticle dispersion. Desired.
得られた金属ナノ粒子は、種々の用途に用いることができるが、特に導電性インクまたは導電性ペーストとして、導電膜形成材料や導体配線形成材料として好適に利用できる。本発明における金属ナノ粒子は粒径が非常に小さく、かつ分散安定性に優れるため、特に導電性インクとして好ましく使用できる。
金属ナノ粒子を含む導電性インクを用いた配線形成方法としては、該導電性インクをインクジェット法により吐出して基板等に着弾させ、着弾したインク滴を焼成して配線を形成させる方法が好ましい。
The obtained metal nanoparticles can be used for various applications, but can be suitably used as a conductive film forming material or a conductive wiring forming material, particularly as a conductive ink or conductive paste. Since the metal nanoparticles in the present invention have a very small particle size and excellent dispersion stability, they can be preferably used particularly as a conductive ink.
As a wiring formation method using a conductive ink containing metal nanoparticles, a method of discharging the conductive ink by an ink jet method to land on a substrate or the like and firing the landed ink droplets to form a wiring is preferable.
以下、実施例により、本発明についてさらに詳細に説明するが、本発明はこれらに限定されるものではない。 EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these.
＜実施例１＞
（Ａ液（銅原料溶液）の調製）
銅原料である硫酸銅五水和物（和光純薬製）２．５ｇ、添加剤である酢酸パラジウム（和光純薬製）２．６ｍｇ、錯化剤である酒石酸ナトリウム二水和物（和光純薬製）２．３ｇ、水酸化ナトリウム２．０g、保護剤であるナチコール１０００（ＷＥＩＳＨＡＲＤＴ製、重量平均分子量２７００のコラーゲンペプチド）２００ｍｇ、純水９０ｍＬを入れ、室温で３０分攪拌して均一な溶液とした。得られた溶液をシリンジに充填し、ＨＡＲＶＡＲＤ社製シリンジポンプにセットした。
なお、Ａ液中における、第１の金属イオンに該当する銅イオンと、第２の金属イオンに該当するパラジウムイオンとの質量比（第２の金属イオンの質量／第１の金属イオンの質量）は、０．００２であった。
<Example 1>
(Preparation of liquid A (copper raw material solution))
Copper sulfate pentahydrate (manufactured by Wako Pure Chemical) 2.5 g, palladium acetate (manufactured by Wako Pure Chemical) 2.6 mg, complexing agent sodium tartrate dihydrate (Wako Pure Chemical) 2.3 g, 2.0 g of sodium hydroxide, 200 mg of Protectol 1000 (made by WEISHARDT, collagen peptide with a weight average molecular weight of 2700) 200 mg and pure water 90 mL are added and stirred at room temperature for 30 minutes to form a homogeneous solution It was. The obtained solution was filled in a syringe and set in a syringe pump manufactured by HARVARD.
In the liquid A, the mass ratio of the copper ion corresponding to the first metal ion and the palladium ion corresponding to the second metal ion (the mass of the second metal ion / the mass of the first metal ion). Was 0.002.
（Ｂ液（還元剤溶液）の調製）
還元剤である水素化ホウ素ナトリウム０．２５ｇおよび水酸化ナトリウム１．０ｇを水３０ｇに溶解し、均一な溶液とした。得られた溶液をシリンジに充填し、ＨＡＲＶＡＲＤ社製シリンジポンプにセットした。
(Preparation of liquid B (reducing agent solution))
0.25 g of sodium borohydride as a reducing agent and 1.0 g of sodium hydroxide were dissolved in 30 g of water to obtain a uniform solution. The obtained solution was filled in a syringe and set in a syringe pump manufactured by HARVARD.
（マイクロリアクターを用いた金属ナノ粒子の合成）
シリンジポンプとリアクターを長さ５０ｃｍ、内径０．５ｍｍのテフロンチューブ（流入路に相当）で連結した。リアクターはＥＹＥＬＡ社製Ｔ字型リアクター（内径０．５ｍｍ）を用いた。なお、該リアクターは、上述した図１で示す、マイクロミキサー（Ｍ）に該当する。リアクターから受け容器までは長さ２０ｃｍ、内径２ｍｍのテフロンチューブで連結した。また、水浴を用いてリアクターを８０℃に加熱した。
シリンジポンプを用いてＡ液（銅原料溶液）を４５ｍＬ/ｍｉｎ、Ｂ液（還元剤溶液）を１５ｍＬ/ｍｉｎで送液して、リアクター内においてＡ液とＢ液を混合して反応させ、チューブの先端より分散液を捕集して、金属ナノ粒子（銅ナノ粒子）を合成した。
なお、本流量におけるレイノルズ数は７００であった。
(Synthesis of metal nanoparticles using a microreactor)
The syringe pump and the reactor were connected with a Teflon tube (corresponding to the inflow path) having a length of 50 cm and an inner diameter of 0.5 mm. The reactor used was a T-shaped reactor (inner diameter 0.5 mm) manufactured by EYELA. The reactor corresponds to the micromixer (M) shown in FIG. 1 described above. The reactor and the receiving container were connected by a Teflon tube having a length of 20 cm and an inner diameter of 2 mm. The reactor was also heated to 80 ° C. using a water bath.
Using a syringe pump, liquid A (copper raw material solution) is fed at 45 mL / min, liquid B (reducing agent solution) is fed at 15 mL / min, liquid A and liquid B are mixed and reacted in the reactor, and tube The dispersion was collected from the tip of the metal to synthesize metal nanoparticles (copper nanoparticles).
The Reynolds number at this flow rate was 700.
＜比較例１：バッチ反応での金属ナノ粒子の合成＞
攪拌機、冷却管を備えた５００ｍｌの三口フラスコに、銅原料である硫酸銅五水和物（和光純薬製）２．５ｇ、添加剤である酢酸パラジウム（和光純薬製）２．６ｍｇ、錯化剤である酒石酸ナトリウム二水和物（和光純薬製）２．３ｇ、水酸化ナトリウム２．０ｇ、保護剤であるナチコール１０００（ＷＥＩＳＨＡＲＤＴ製、重量平均分子量２７００のコラーゲンペプチド）２００ｍｇ、純水９０ｍＬを入れ、室温で３０分攪拌して均一な溶液とした。次いで、還元剤である水素化ホウ素ナトリウム０．２５ｇおよび水酸化ナトリウム１．０ｇを水３０ｇに溶解し、得られた水溶液を上記溶液に５ｍＬ/ｍｉｎの滴下速度で滴下し、さらに室温で２時間反応を行い、金属ナノ粒子を合成した。
<Comparative Example 1: Synthesis of metal nanoparticles by batch reaction>
In a 500 ml three-necked flask equipped with a stirrer and a condenser, 2.5 g of copper sulfate pentahydrate (manufactured by Wako Pure Chemical) as a copper raw material, 2.6 mg of palladium acetate (manufactured by Wako Pure Chemical) as an additive, complex Sodium tartrate dihydrate (manufactured by Wako Pure Chemical) 2.3 g, sodium hydroxide 2.0 g, protective agent Nachicol 1000 (WEISHARDT, collagen peptide with a weight average molecular weight of 2700) 200 mg, pure water 90 mL And stirred at room temperature for 30 minutes to obtain a uniform solution. Next, 0.25 g of sodium borohydride and 1.0 g of sodium hydroxide as reducing agents were dissolved in 30 g of water, and the obtained aqueous solution was dropped into the above solution at a dropping rate of 5 mL / min, and further at room temperature for 2 hours. Reaction was performed to synthesize metal nanoparticles.
＜粒径評価＞
実施例１および比較例１で得られた金属ナノ粒子分散液中の金属ナノ粒子の二次粒子径を、Marveln社製動的光散乱測定装置（ゼータサイザーＺＳ）にて測定した。
実施例１において得られた金属ナノ粒子の二次粒子径（数平均粒子径）が約２０ｎｍであったのに対し、比較例１において得られた金属ナノ粒子の二次粒子径（数平均粒子径）は約２０００μｍであった。
<Evaluation of particle size>
The secondary particle diameter of the metal nanoparticles in the metal nanoparticle dispersion liquid obtained in Example 1 and Comparative Example 1 was measured with a Marveln dynamic light scattering measurement device (Zetasizer ZS).
The secondary particle diameter (number average particle diameter) of the metal nanoparticles obtained in Example 1 was about 20 nm, whereas the secondary particle diameter (number average particle) of the metal nanoparticles obtained in Comparative Example 1 was about 20 nm. (Diameter) was about 2000 μm.
＜純度測定＞
実施例１および比較例１で得られた金属ナノ粒子分散液中の金属ナノ粒子の純度を、限外ろ過およびＩＣＰを用いて測定した。
すなわち、実施例１および比較例１で得られた金属ナノ粒子分散液を限外ろ過して濃縮し、金属ナノ粒子分散液から除去したろ液に銅およびパラジウムがほぼ含まれていないことをＩＣＰで確認することで、仕込んだ銅およびパラジウムはほぼ全て分散液中に存在すること、すなわち、実施例１および比較例１の分散液は共に、Ａ液中における銅イオンとパラジウムイオンとの仕込み比と略同じ組成を有し、銅原子の純度が高いことが確認された。なお、限外ろ過の前後で粒子の凝集がないことは光散乱の測定より確認した。
<Purity measurement>
The purity of the metal nanoparticles in the metal nanoparticle dispersion obtained in Example 1 and Comparative Example 1 was measured using ultrafiltration and ICP.
That is, the metal nanoparticle dispersion obtained in Example 1 and Comparative Example 1 was ultrafiltered and concentrated, and the filtrate removed from the metal nanoparticle dispersion was substantially free of copper and palladium. It is confirmed that almost all of the charged copper and palladium are present in the dispersion, that is, both of the dispersions of Example 1 and Comparative Example 1 are charged ratios of copper ions and palladium ions in the liquid A. It was confirmed that the purity of copper atoms is high. In addition, it was confirmed by light scattering measurement that there was no aggregation of particles before and after ultrafiltration.
１，２ マイクロリアクターへの原料供給口
３，４ マイクロミキサーへの原料供給口
５ Ａ液およびＢ液の混合開始点
６ マイクロリアクターの出口
1, 2 Raw material supply port to
Claims (3)
Ａ液：第１の金属イオンと、前記第１の金属イオンの酸化還元電位よりも高い酸化還元電位を有する第２の金属イオンとを含み、前記第２の金属イオンの含有質量と前記第１の金属イオンの含有質量との比（第２の金属イオンの含有質量／第１の金属イオンの含有質量）が０．００５以下である溶液
Ｂ液：前記第１の金属イオンおよび前記第２の金属イオンを還元する還元剤を含む溶液
前記第１の金属イオンが、銅イオンであり、
前記金属ナノ粒子の二次粒子径が１００ｎｍ以下である、金属ナノ粒子の製造方法。
なお、Ａ液およびＢ液の少なくともいずれか一方には、分散剤が含まれる。 A method for producing metal nanoparticles, wherein a metal nanoparticle is produced by mixing the following liquid A and liquid B using a microreactor ,
Liquid A: containing a first metal ion and a second metal ion having a redox potential higher than the redox potential of the first metal ion, the contained mass of the second metal ion and the first metal ion Solution B solution having a ratio of the metal ion content to the second metal ion content (the second metal ion content / the first metal ion content) is 0.005 or less: the first metal ion and the second metal ion Solution containing a reducing agent that reduces metal ions
The first metal ion is a copper ion;
The manufacturing method of the metal nanoparticle whose secondary particle diameter of the said metal nanoparticle is 100 nm or less.
In addition, a dispersing agent is contained in at least any one of A liquid and B liquid.
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