JP2009035781A - Method for producing metal nanoparticle - Google Patents
Method for producing metal nanoparticle Download PDFInfo
- Publication number
- JP2009035781A JP2009035781A JP2007201910A JP2007201910A JP2009035781A JP 2009035781 A JP2009035781 A JP 2009035781A JP 2007201910 A JP2007201910 A JP 2007201910A JP 2007201910 A JP2007201910 A JP 2007201910A JP 2009035781 A JP2009035781 A JP 2009035781A
- Authority
- JP
- Japan
- Prior art keywords
- metal
- ion
- nanoparticles
- metal nanoparticles
- suspension
- 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.)
- Granted
Links
- 239000002082 metal nanoparticle Substances 0.000 title claims abstract description 62
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 46
- 150000001875 compounds Chemical class 0.000 claims abstract description 49
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 37
- 125000000962 organic group Chemical group 0.000 claims abstract description 10
- 230000033116 oxidation-reduction process Effects 0.000 claims abstract description 5
- 229910052751 metal Inorganic materials 0.000 claims description 41
- 239000002184 metal Substances 0.000 claims description 41
- 239000003638 chemical reducing agent Substances 0.000 claims description 34
- 150000003839 salts Chemical class 0.000 claims description 20
- -1 trifluoroacetate ion Chemical class 0.000 claims description 20
- 150000001450 anions Chemical class 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 4
- 239000000725 suspension Substances 0.000 abstract description 30
- 238000000034 method Methods 0.000 abstract description 11
- 239000012535 impurity Substances 0.000 abstract description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052799 carbon Inorganic materials 0.000 abstract description 3
- AQRLNPVMDITEJU-UHFFFAOYSA-N triethylsilane Chemical compound CC[SiH](CC)CC AQRLNPVMDITEJU-UHFFFAOYSA-N 0.000 description 32
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 19
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 17
- 239000002245 particle Substances 0.000 description 17
- 238000006243 chemical reaction Methods 0.000 description 16
- 239000002904 solvent Substances 0.000 description 16
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 15
- 239000000243 solution Substances 0.000 description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 239000002105 nanoparticle Substances 0.000 description 12
- 239000006185 dispersion Substances 0.000 description 10
- 239000010419 fine particle Substances 0.000 description 10
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical compound [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 description 10
- 229940071536 silver acetate Drugs 0.000 description 10
- 238000001704 evaporation Methods 0.000 description 9
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- 150000003377 silicon compounds Chemical class 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- 239000000460 chlorine Substances 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 229910052763 palladium Inorganic materials 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 230000008020 evaporation Effects 0.000 description 6
- 239000004973 liquid crystal related substance Substances 0.000 description 6
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 description 6
- 230000001603 reducing effect Effects 0.000 description 6
- 229910052709 silver Inorganic materials 0.000 description 6
- 239000004332 silver Substances 0.000 description 6
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 5
- 238000009835 boiling Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000010931 gold Substances 0.000 description 4
- 150000003961 organosilicon compounds Chemical class 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- 229920000191 poly(N-vinyl pyrrolidone) Polymers 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 3
- JCFNZIBTMUOXRK-UHFFFAOYSA-N CCCCCCCCCCCC[SiH](C)C Chemical compound CCCCCCCCCCCC[SiH](C)C JCFNZIBTMUOXRK-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 3
- 229940006460 bromide ion Drugs 0.000 description 3
- 239000000084 colloidal system Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 125000002524 organometallic group Chemical group 0.000 description 3
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000012266 salt solution Substances 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- PMBXCGGQNSVESQ-UHFFFAOYSA-N 1-Hexanethiol Chemical compound CCCCCCS PMBXCGGQNSVESQ-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- 239000005212 4-Cyano-4'-pentylbiphenyl Substances 0.000 description 2
- HHPCNRKYVYWYAU-UHFFFAOYSA-N 4-cyano-4'-pentylbiphenyl Chemical group C1=CC(CCCCC)=CC=C1C1=CC=C(C#N)C=C1 HHPCNRKYVYWYAU-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 239000005046 Chlorosilane Substances 0.000 description 2
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- FZERHIULMFGESH-UHFFFAOYSA-N N-phenylacetamide Chemical compound CC(=O)NC1=CC=CC=C1 FZERHIULMFGESH-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- UWAXDPWQPGZNIO-UHFFFAOYSA-N benzylsilane Chemical compound [SiH3]CC1=CC=CC=C1 UWAXDPWQPGZNIO-UHFFFAOYSA-N 0.000 description 2
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 2
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- AHQMQQYLFHXPOE-UHFFFAOYSA-N decyl(dimethyl)silicon Chemical compound CCCCCCCCCC[Si](C)C AHQMQQYLFHXPOE-UHFFFAOYSA-N 0.000 description 2
- 239000011903 deuterated solvents Substances 0.000 description 2
- 150000002009 diols Chemical class 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 238000009434 installation Methods 0.000 description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 description 2
- 229940006461 iodide ion Drugs 0.000 description 2
- QPJVMBTYPHYUOC-UHFFFAOYSA-N methyl benzoate Chemical compound COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 description 2
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 2
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- 230000009965 odorless effect Effects 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- PARWUHTVGZSQPD-UHFFFAOYSA-N phenylsilane Chemical compound [SiH3]C1=CC=CC=C1 PARWUHTVGZSQPD-UHFFFAOYSA-N 0.000 description 2
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- BGHCVCJVXZWKCC-UHFFFAOYSA-N tetradecane Chemical compound CCCCCCCCCCCCCC BGHCVCJVXZWKCC-UHFFFAOYSA-N 0.000 description 2
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- IIYFAKIEWZDVMP-UHFFFAOYSA-N tridecane Chemical compound CCCCCCCCCCCCC IIYFAKIEWZDVMP-UHFFFAOYSA-N 0.000 description 2
- PQDJYEQOELDLCP-UHFFFAOYSA-N trimethylsilane Chemical compound C[SiH](C)C PQDJYEQOELDLCP-UHFFFAOYSA-N 0.000 description 2
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- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
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- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- 125000001340 2-chloroethyl group Chemical group [H]C([H])(Cl)C([H])([H])* 0.000 description 1
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- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
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- JAJIPIAHCFBEPI-UHFFFAOYSA-N 9,10-dioxoanthracene-1-sulfonic acid Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2S(=O)(=O)O JAJIPIAHCFBEPI-UHFFFAOYSA-N 0.000 description 1
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- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
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- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- VQPFDLRNOCQMSN-UHFFFAOYSA-N bromosilane Chemical compound Br[SiH3] VQPFDLRNOCQMSN-UHFFFAOYSA-N 0.000 description 1
- GJELMAGYBYKKQI-UHFFFAOYSA-N butan-2-yl(diethyl)silane Chemical compound CCC(C)[SiH](CC)CC GJELMAGYBYKKQI-UHFFFAOYSA-N 0.000 description 1
- ISRXAIWFKZXWND-UHFFFAOYSA-N butan-2-yl(dipropyl)silane Chemical compound CCC[SiH](CCC)C(C)CC ISRXAIWFKZXWND-UHFFFAOYSA-N 0.000 description 1
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Abstract
Description
本発明は、溶液中で金属塩を還元して金属ナノ粒子の懸濁液を製造する方法に係り、特に、懸濁液から余剰還元剤等の夾雑物を効率よく除去して金属ナノ粒子の純度を容易に高めることが可能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 a suspension of metal nanoparticles by reducing a metal salt in a solution, and in particular, by removing impurities such as excess reducing agent from the suspension efficiently. The present invention relates to a method for producing metal nanoparticles capable of easily increasing the purity.
粒径がおよそ数ｎｍ〜数１００ｎｍ程度の金属の微粒子のことを金属ナノ粒子という。金属ナノ粒子は、このように粒径が小さいことに起因する種々の特性を有しており、従来、様々な分野で利用されている。例えば、マトリクス表示液晶ディスプレイ等においては、液晶セルに充填された液晶に金属ナノ粒子を添加することにより、液晶素子の応答が高速化することが知られている。また、金属ナノ粒子は、通常のサブミクロン以上の塊状の金属に比べて焼結温度が低いことから、配線材料としてプリント配線板と電子部品の接続等に用いられている。 Metal fine particles having a particle size of about several nanometers to several hundred nanometers are referred to as metal nanoparticles. Metal nanoparticles have various properties resulting from such a small particle size and have been used in various fields. For example, in a matrix display liquid crystal display or the like, it is known that the response of the liquid crystal element is increased by adding metal nanoparticles to the liquid crystal filled in the liquid crystal cell. In addition, metal nanoparticles are used as a wiring material for connecting a printed wiring board and an electronic component because the sintering temperature is lower than that of a normal metal of submicron or more.
金属ナノ粒子の製造方法としては、例えば、坩堝に入れて加熱した原料固体から発生した蒸気に対して不活性ガスの分子等を衝突させて急冷することにより微粒子化するガス中蒸発法が知られている。この方法によれば、高濃度かつ高純度の金属ナノ粒子を得ることができる。しかしながら、原料固体から蒸気を発生させるための設備が必要であるため、金属ナノ粒子を安価に製造することができないという課題があった。そこで、このような特別な設備を必要としないものとして、溶液中で金属塩を還元して金属ナノ粒子を製造する方法が注目されている。 As a method for producing metal nanoparticles, for example, a gas evaporation method is known in which particles of an inert gas collide with vapor generated from a raw material solid heated in a crucible and rapidly cooled by colliding with the gas. ing. According to this method, high concentration and high purity metal nanoparticles can be obtained. However, since equipment for generating steam from the raw material solid is required, there is a problem that metal nanoparticles cannot be produced at low cost. Thus, as a method that does not require such special equipment, a method of producing metal nanoparticles by reducing a metal salt in a solution has attracted attention.
例えば、特許文献１には、「高濃度金属微粒子分散液の製造方法」という名称で、有機酸の存在下で有機金属塩を還元することにより、金属微粒子分散液を製造する方法に関する発明が開示されている。
特許文献１に開示された発明である金属微粒子分散液の製造方法は、有機金属塩を炭素数１０以下の有機酸が有機金属塩と等モル以上含有された溶媒に溶解させて、金属換算濃度が少なくとも１質量％となるように調製された有機金属塩溶液をジオール又はヒドラジン又はヒドロキシルアミンで還元することを特徴としている。
上記製造方法によれば、高濃度の有機金属塩溶液が生成されるとともに、還元剤により、この有機金属塩溶液に対し強い還元作用が発揮される。また、還元後に金属イオンが残留し難いという作用を有する。したがって、高濃度の金属微粒子分散液を容易に製造することができる。
For example, Patent Document 1 discloses an invention relating to a method for producing a metal fine particle dispersion by reducing an organic metal salt in the presence of an organic acid under the name “method for producing a high concentration metal fine particle dispersion”. Has been.
In the method for producing a metal fine particle dispersion which is an invention disclosed in Patent Document 1, an organic metal salt is dissolved in a solvent containing an organic acid having 10 or less carbon atoms in an equimolar amount or more with an organic metal salt to obtain a metal equivalent concentration. It is characterized in that an organometallic salt solution prepared so as to be at least 1% by mass is reduced with diol, hydrazine or hydroxylamine.
According to the above production method, a highly concentrated organometallic salt solution is produced, and a strong reducing action is exerted on the organometallic salt solution by the reducing agent. In addition, it has an effect that metal ions hardly remain after reduction. Therefore, a high concentration fine metal particle dispersion can be easily produced.
特許文献２には、「金属ナノ粒子及び金属ナノ粒子分散液の製造方法」という名称で、高価な設備を必要とせずに高濃度の金属ナノ粒子分散液を簡便且つ安価に連続して得ることのできる金属ナノ粒子及び金属ナノ粒子分散液の製造方法に関する発明が開示されている。
特許文献２に開示された発明である金属ナノ粒子及び金属ナノ粒子分散液の製造方法は、少なくとも１種の金属イオンと有機分子からなる保護剤が混合された溶液を溶媒下で還元するとともに、有機分子で保護された金属ナノ粒子集合体を沈降させて回収するものである。
上記製造方法によれば、生成された金属ナノ粒子は有機分子で保護されているため、溶媒に対する親和性が低下して集合体となって沈降するという作用を有する。これにより、金属ナノ粒子集合体を連続して回収することができる。
Patent Document 2 discloses that a metal nanoparticle dispersion having a high concentration can be continuously obtained simply and inexpensively without the need for expensive equipment, under the name of “method for producing metal nanoparticles and metal nanoparticle dispersion”. An invention relating to a method for producing metal nanoparticles and metal nanoparticle dispersions that can be produced is disclosed.
In the method for producing metal nanoparticles and metal nanoparticle dispersion, which is an invention disclosed in Patent Document 2, a solution in which a protective agent composed of at least one metal ion and an organic molecule is mixed is reduced under a solvent, A metal nanoparticle aggregate protected by organic molecules is precipitated and recovered.
According to the said manufacturing method, since the produced | generated metal nanoparticle is protected by the organic molecule, it has the effect | action that the affinity with respect to a solvent falls and it precipitates as an aggregate. Thereby, a metal nanoparticle aggregate | assembly can be collect | recovered continuously.
特許文献３には、「金属コロイド溶液の製造方法」という名称で、均一な粒子径を有する金属コロイド微粒子が単分散した溶液を容易に製造可能な方法に関する発明が開示されている。
特許文献３に開示された発明である金属コロイド溶液の製造方法は、標準水素電極電位が−０．８〜＋１．２ｅＶの範囲にある金属塩、安定化剤及び溶媒を混合して調製した金属コロイド溶液調製用母液を、１０〜９５℃の温度に調整し、さらに、標準水素電極電位が−０．２〜＋１．５ｅＶの範囲にあり、かつ上記金属塩を構成する金属よりも標準水素電極電位が高い金属塩を添加するとともに、還元剤を用いてこれら２種類の金属塩を還元することを特徴としている。
このような製造方法によれば、標準水素電極電位が−０．８〜＋１．５ｅＶの範囲にある金属からなる核微粒子の表面に、この核微粒子よりも標準水素電極電位が高く、かつ標準水素電極電位が−０．８〜＋１．２ｅＶの範囲にある金属が析出した複合金属微粒子が分散したコロイド溶液が生成される。そして、このコロイド溶液中には、粒径分布が狭く、大きさが揃った金属コロイド微粒子が単分散している。すなわち、本製造方法によれば、均一な粒子径を有する金属コロイド微粒子が単分散した溶液を製造することが可能である。
Patent Document 3 discloses an invention relating to a method capable of easily producing a solution in which metal colloidal fine particles having a uniform particle diameter are monodispersed under the name “method for producing a metal colloid solution”.
The method for producing a metal colloid solution according to the invention disclosed in Patent Document 3 is a metal prepared by mixing a metal salt, a stabilizer and a solvent having a standard hydrogen electrode potential in the range of -0.8 to +1.2 eV. The colloidal solution preparing mother liquor is adjusted to a temperature of 10 to 95 ° C., and the standard hydrogen electrode potential is in the range of −0.2 to +1.5 eV, and the standard hydrogen electrode is higher than the metal constituting the metal salt. It is characterized by adding a metal salt having a high potential and reducing these two kinds of metal salts using a reducing agent.
According to such a manufacturing method, the standard hydrogen electrode potential is higher than the nuclear fine particles on the surface of the nuclear fine particles made of a metal having a standard hydrogen electrode potential in the range of −0.8 to +1.5 eV, and A colloidal solution is produced in which composite metal fine particles in which a metal having an electrode potential in the range of −0.8 to +1.2 eV is deposited are dispersed. In this colloid solution, metal colloidal fine particles having a narrow particle size distribution and uniform size are monodispersed. That is, according to this production method, it is possible to produce a solution in which metal colloidal fine particles having a uniform particle diameter are monodispersed.
上述の従来技術である特許文献１に開示された発明においては、還元剤としてジオールを用いた場合、反応させる際の温度を１００℃以上にしなければならず、そのための設備を必要とする。また、ヒドラジンやヒドロキシルアミンは刺激臭を有するため、取扱いが容易でないという課題があった。 In the invention disclosed in Patent Document 1 which is the above-described prior art, when diol is used as a reducing agent, the temperature at the time of reaction must be 100 ° C. or higher, and equipment for that is required. Further, since hydrazine and hydroxylamine have an irritating odor, there is a problem that handling is not easy.
また、特許文献２及び特許文献３に開示された発明においては、水素化ホウ素ナトリウムを還元剤として利用するため、夾雑物が塩となる。この場合、脱塩操作を行うための設備が必要となり、製造コストが高くなるという課題があった。 In the inventions disclosed in Patent Document 2 and Patent Document 3, since sodium borohydride is used as a reducing agent, impurities are converted into salts. In this case, equipment for performing the desalting operation is required, and there is a problem that the manufacturing cost increases.
本発明はかかる従来の事情に対処してなされたものであり、安全かつ安価に金属ナノ粒子の懸濁液を製造し、この懸濁液から夾雑物を効率よく除去して高純度の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。 The present invention has been made in response to such a conventional situation. A metal nanoparticle suspension is produced safely and inexpensively, and impurities are efficiently removed from the suspension to obtain high-purity metal nanoparticle. An object is to provide a method for producing particles.
上記目的を達成するため、請求項１記載の発明である金属ナノ粒子の製造方法は、金属イオンに還元剤を反応させて金属ナノ粒子を製造する方法において、金属イオンの標準酸化還元電位は０Ｖ以上であり、還元剤は一般式（１）で示されるモノヒドロシラン化合物であることを特徴とするものである。 In order to achieve the above object, the method for producing metal nanoparticles according to claim 1 is a method for producing metal nanoparticles by reacting a metal ion with a reducing agent, wherein the standard redox potential of the metal ions is 0V. As described above, the reducing agent is a monohydrosilane compound represented by the general formula (1).
このような製造方法によれば、標準酸化還元電位が０Ｖよりも小さいヒドロシラン化合物が金属イオンを還元し、金属ナノ粒子の懸濁液を生成するという作用を有する。なお、ヒドロシラン化合物はほとんど無臭であり、刺激臭がないため、安全である。また、金属イオンが還元される際に、沸点の低い有機ケイ素化合物が生成されるという作用を有する。さらに、還元剤として使用される上記モノヒドロシラン化合物は蒸発し易いという特性を有する。従って、懸濁液中に残留する有機ケイ素化合物や余剰還元剤などの夾雑物は、蒸発によって容易に除去される。 According to such a manufacturing method, a hydrosilane compound having a standard oxidation-reduction potential smaller than 0 V has an action of reducing metal ions and generating a suspension of metal nanoparticles. Hydrosilane compounds are safe because they are almost odorless and have no pungent odor. Moreover, it has the effect | action that an organosilicon compound with a low boiling point is produced | generated when a metal ion is reduce | restored. Furthermore, the monohydrosilane compound used as a reducing agent has a characteristic that it easily evaporates. Therefore, impurities such as organosilicon compounds and excess reducing agent remaining in the suspension are easily removed by evaporation.
請求項２記載の発明は、請求項１記載の金属ナノ粒子の製造方法において、モノヒドロシラン化合物に含まれる有機基は、無置換のアルキル基であることを特徴とするものである。
無置換のアルキル基を有機基として含むモノヒドロシラン化合物は製造性及び取扱い性に優れている。従って、このようなモノヒドロシラン化合物を還元剤として使用する上記製造方法によれば、還元剤の調達が容易であるとともに、製造工程における作業効率が向上する。
The invention according to claim 2 is the method for producing metal nanoparticles according to claim 1, wherein the organic group contained in the monohydrosilane compound is an unsubstituted alkyl group.
A monohydrosilane compound containing an unsubstituted alkyl group as an organic group is excellent in manufacturability and handleability. Therefore, according to the manufacturing method using such a monohydrosilane compound as a reducing agent, it is easy to procure the reducing agent and work efficiency in the manufacturing process is improved.
請求項３記載の発明は、請求項１又は請求項２に記載の金属ナノ粒子の製造方法において、金属イオンは金属塩からの電離によって生成され、この金属塩から金属イオンともに電離する陰イオンは、酢酸イオン、トリフルオロ酢酸イオン、塩化物イオン、フッ化物イオンから選ばれる少なくとも１種であることを特徴とするものである。
このような製造方法においては、金属イオンが還元される際に、加水分解し難く、空気中の湿気に対して強いケイ素化合物が生成されるという作用を有する。
According to a third aspect of the present invention, in the method for producing metal nanoparticles according to the first or second aspect, the metal ion is generated by ionization from the metal salt, and the anion ionized together with the metal ion from the metal salt is , Acetate ion, trifluoroacetate ion, chloride ion, and fluoride ion.
Such a production method has an effect that when a metal ion is reduced, a silicon compound that is hardly hydrolyzed and strong against moisture in the air is generated.
以上説明したように、本発明の請求項１に記載の金属ナノ粒子の製造方法によれば、還元剤の取扱いが容易であるため、安全かつ効率的に製造作業を行うことができる。また、有機ケイ素化合物や余剰還元剤などの夾雑物を蒸発により容易に除去することができる。従って、懸濁液中の金属ナノ粒子の純度を効率よく高めることができる。 As described above, according to the method for producing metal nanoparticles according to claim 1 of the present invention, since the handling of the reducing agent is easy, the production operation can be performed safely and efficiently. Further, impurities such as organosilicon compounds and excess reducing agent can be easily removed by evaporation. Therefore, the purity of the metal nanoparticles in the suspension can be increased efficiently.
本発明の請求項２に記載の金属ナノ粒子の製造方法においては、材料コスト及び製造コストの削減を図ることが可能である。 In the method for producing metal nanoparticles according to claim 2 of the present invention, it is possible to reduce the material cost and the production cost.
本発明の請求項３に記載の金属ナノ粒子の製造方法においては、製造環境を無水条件に設定する必要がないため、乾燥設備の設置等による余分な設備費用が発生しない。従って、金属ナノ粒子を安価に製造することが可能である。 In the method for producing metal nanoparticles according to claim 3 of the present invention, it is not necessary to set the production environment to anhydrous conditions, and therefore no extra equipment costs are required due to the installation of drying equipment or the like. Therefore, it is possible to produce metal nanoparticles at a low cost.
以下に、本発明の最良の実施の形態に係る金属ナノ粒子の製造方法の実施例について説明する。 Below, the Example of the manufacturing method of the metal nanoparticle which concerns on the best embodiment of this invention is described.
本実施例の金属ナノ粒子の製造方法は、ヒドロシラン化合物によって金属イオンを溶液中で還元し、金属ナノ粒子の懸濁液を製造することを特徴とする。
ヒドロシラン化合物は、ケイ素原子（Ｓｉ）の有する４つの結合手のうち、少なくとも１つの結合手に水素原子（Ｈ）が直接結合したものであり、この水素原子の数によって区別され、それぞれモノヒドロシラン（Ｈが１つ）、ジヒドロシラン（Ｈが２つ）、トリヒドロシラン（Ｈが３つ）と呼ばれている。そして、ヒドロシラン化合物はほとんど無臭であり、刺激臭を伴わないため、取扱いが容易である。従って、ヒドロシラン化合物を還元剤として用いることによれば、金属ナノ粒子を安全かつ効率よく製造することができる。
このように、上記３種類のヒドロシラン化合物はいずれも還元剤として優れた特性を有している。しかし、ジヒドロシラン化合物及びトリヒドロシラン化合物を還元剤として使用する場合、モノヒドロシラン化合物を還元剤として使用する場合と比べると、金属ナノ粒子と同時に生成されるケイ素化合物が蒸発し難いものとなる。従って、本願発明の金属ナノ粒子の製造に用いる還元剤としてはモノヒドロシラン化合物の方がより好ましい。なお、本実施例では、特に、以下の一般式（１）で示されるモノヒドロシラン化合物を用いている。
The method for producing metal nanoparticles of this example is characterized in that metal ions are reduced in a solution by a hydrosilane compound to produce a suspension of metal nanoparticles.
The hydrosilane compound is one in which a hydrogen atom (H) is directly bonded to at least one of the four bonds of the silicon atom (Si), and is distinguished by the number of hydrogen atoms. One H), dihydrosilane (two H), and trihydrosilane (three H). And since a hydrosilane compound is almost odorless and does not accompany an irritating odor, it is easy to handle. Therefore, by using a hydrosilane compound as a reducing agent, metal nanoparticles can be produced safely and efficiently.
Thus, all of the above three types of hydrosilane compounds have excellent properties as reducing agents. However, when a dihydrosilane compound and a trihydrosilane compound are used as the reducing agent, the silicon compound generated simultaneously with the metal nanoparticles is less likely to evaporate than when a monohydrosilane compound is used as the reducing agent. Therefore, the monohydrosilane compound is more preferable as the reducing agent used for producing the metal nanoparticles of the present invention. In this example, in particular, a monohydrosilane compound represented by the following general formula (1) is used.
一般式（１）において、モノヒドロシラン化合物の製造性及び取扱い性が容易であるという理由から、有機基は無置換のアルキル基を有するものであることが望ましい。この場合、還元剤の調達が容易となるとともに、製造工程における作業効率が向上する。従って、材料コスト及び製造コストの削減を図ることができる。
なお、アルキル基とは、炭素原子が１列に結合した、いわゆる脂肪族炭化水素から１個の水素原子（Ｈ）を取り去った原子団の総称のことである。このようなアルキル基としては、メチル基（−ＣＨ３）、エチル基（−Ｃ２Ｈ５）、プロピル基（−Ｃ３Ｈ７）、ブチル基（−Ｃ４Ｈ９）、ペンチル基（−Ｃ５Ｈ１１）、ヘキシル基（−Ｃ６Ｈ１３）、フェニル基（−Ｃ６Ｈ５）、シクロヘキシル基（−Ｃ６Ｈ１１）などが例示される。なお、ケイ素化合物自体の安定性を損なわないものであれば、これらの有機基以外にも、例えば、ハロゲン原子（周期表の１７族のフッ素（Ｆ）、塩素（Ｃｌ）、臭素（Ｂｒ）、ヨウ素（Ｉ）の４元素を含む化合物の総称）、アルコキシ基（アルコールの水酸基から水素を取り除いた官能基）、シアノ基（−ＣＮ）等の各種官能基やヘテロ原子（水素と炭素以外の原子）又は不飽和結合を有するものを用いても良い。また、ハロゲン原子で置換された、フルオロメチル基（−ＣＨ２Ｆ）、クロロメチル基（−ＣＨ２Ｃｌ）、２−クロロエチル基（−Ｃ２Ｈ４Ｃｌ）等のアルキル基やアルコキシ基で置換された、メトキシメチル基（−ＣＨ２ＯＣＨ３）、メトキシエチル基（−ＣＨ２ＣＨ２ＯＣＨ３）、２−エトキシエチル基（−Ｃ２Ｈ４ＯＣ２Ｈ５）等のアルキル基を用いることもできる。
In the general formula (1), it is desirable that the organic group has an unsubstituted alkyl group because it is easy to produce and handle the monohydrosilane compound. In this case, it becomes easy to procure the reducing agent and work efficiency in the manufacturing process is improved. Accordingly, the material cost and the manufacturing cost can be reduced.
The alkyl group is a general term for an atomic group in which one hydrogen atom (H) is removed from a so-called aliphatic hydrocarbon in which carbon atoms are bonded in one row. Examples of such an alkyl group include a methyl group (—CH 3 ), an ethyl group (—C 2 H 5 ), a propyl group (—C 3 H 7 ), a butyl group (—C 4 H 9 ), and a pentyl group (— C 5 H 11 ), hexyl group (—C 6 H 13 ), phenyl group (—C 6 H 5 ), cyclohexyl group (—C 6 H 11 ) and the like are exemplified. As long as the stability of the silicon compound itself is not impaired, other than these organic groups, for example, a halogen atom (group 17 fluorine (F), chlorine (Cl), bromine (Br), Various functional groups such as iodine (I) containing four elements, alkoxy groups (functional groups obtained by removing hydrogen from alcohol hydroxyl groups), cyano groups (-CN), and hetero atoms (atoms other than hydrogen and carbon) ) Or those having an unsaturated bond may be used. In addition, substituted with an alkyl group or an alkoxy group such as a fluoromethyl group (—CH 2 F), a chloromethyl group (—CH 2 Cl), or a 2-chloroethyl group (—C 2 H 4 Cl) substituted with a halogen atom Alkyl groups such as methoxymethyl group (—CH 2 OCH 3 ), methoxyethyl group (—CH 2 CH 2 OCH 3 ), 2-ethoxyethyl group (—C 2 H 4 OC 2 H 5 ), etc. You can also.
なお、合成の容易さ及び金属イオンとの反応生成物の沸点の低さ（蒸発除去の容易さ）等の理由から、一般式（１）のＲ１、Ｒ２、Ｒ３の炭素数は１乃至８よりも１乃至４である方がさらに望ましい。このようなものとしては、例えば、トリメチルシラン、ジメチルエチルシラン、ジエチルメリルシラン、トリエチルシラン、ビニルジメチルシラン、ジビニルメチルシラン、トリビニルシラン、ジメチルプロピルシラン、ジプロピルメチルシラン、トリプロピルシラン、ジメチルイソプロピルシラン、ジイソプロピルメチルシラン、トリイソプロピルシラン、ブチルジメチルシラン、ジブチルメチルシラン、ブチルジエチルシラン、ジブチルエチルシラン、ブチルジプロピルシラン、ブチルジイソプロピルシラン、ジブチルプロピルシラン、ジブチルイソプロピルシラン、ブチルエチルメチルシラン、ブチルエチルプロピルシラン、ブチルエチルイソプロピルシラン、ブチルメチルイソプロピルシラン、トリブチルシラン、ｓｅｃ−ブチルジメチルシラン、ジｓｅｃ−ブチルメチルシラン、ｓｅｃ−ブチルジエチルシラン、ジｓｅｃ−ブチルエチルシラン、ｓｅｃ−ブチルジプロピルシラン、ｓｅｃ−ブチルジイソプロピルシラン、ジｓｅｃ−ブチルプロピルシラン、ジｓｅｃ−ブチルイソプロピルシラン、ｓｅｃ−ブチルエチルメチルシラン、ｓｅｃ−ブチルエチルプロピルシラン、ｓｅｃ−ブチルエチルイソプロピルシラン、ｓｅｃ−ブチルメチルイソプロピルシラン、トリｓｅｃ−ブチルシラン、ｔｅｒｔ−ブチルジメチルシラン、ジｔｅｒｔ−ブチルメチルシラン、ｔｅｒｔ−ブチルジエチルシラン、ジｔｅｒｔ−ブチルエチルシラン、ｔｅｒｔ−ブチルジプロピルシラン、ｔｅｒｔ−ブチルジイソプロピルシラン、ジｔｅｒｔ−ブチルプロピルシラン、ジｔｅｒｔ−ブチルイソプロピルシラン、ｔｅｒｔ−ブチルエチルメチルシラン、ｔｅｒｔ−ブチルエチルプロピルシラン、ｔｅｒｔ−ブチルエチルイソプロピルシラン、ｔｅｒｔ−ブチルメチルイソプロピルシラン、トリｔｅｒｔ−ブチルシランなどがある。なお、これらのモノヒドロシラン化合物の標準酸化還元電位はおよそ−０．４〜０Ｖである。したがって、これらのモノヒドロシラン化合物によって還元されるべき金属イオンは標準酸化還元電位が０Ｖ以上のものでなければならない。なお、金属塩からの電離によって生成される金属イオンの標準酸化還元電位は、サイクリックボルタンメトリー等の測定法により測定することができる。 Note that, for reasons such as ease of synthesis and low boiling point of the reaction product with metal ions (ease of evaporative removal), the carbon number of R 1 , R 2 and R 3 in the general formula (1) is 1 1 to 4 is more desirable than to 8. Such as, for example, trimethylsilane, dimethylethylsilane, diethylmerylsilane, triethylsilane, vinyldimethylsilane, divinylmethylsilane, trivinylsilane, dimethylpropylsilane, dipropylmethylsilane, tripropylsilane, dimethylisopropylsilane , Diisopropylmethylsilane, triisopropylsilane, butyldimethylsilane, dibutylmethylsilane, butyldiethylsilane, dibutylethylsilane, butyldipropylsilane, butyldiisopropylsilane, dibutylpropylsilane, dibutylisopropylsilane, butylethylmethylsilane, butylethylpropyl Silane, butyl ethyl isopropyl silane, butyl methyl isopropyl silane, tributyl silane, sec-butyl di Tilsilane, disec-butylmethylsilane, sec-butyldiethylsilane, disec-butylethylsilane, sec-butyldipropylsilane, sec-butyldiisopropylsilane, disec-butylpropylsilane, disec-butylisopropylsilane, sec -Butylethylmethylsilane, sec-butylethylpropylsilane, sec-butylethylisopropylsilane, sec-butylmethylisopropylsilane, trisec-butylsilane, tert-butyldimethylsilane, ditert-butylmethylsilane, tert-butyldiethylsilane Di-tert-butylethylsilane, tert-butyldipropylsilane, tert-butyldiisopropylsilane, ditert-butylpropylsilane, ditert-butyl Triisopropylsilane, tert- butyl ethyl methyl silane, tert- butyl ethyl propyl silane, tert- butyl ethyl isopropyl silane, tert- butyl methyl isopropyl silane, and the like birds tert- butyl silane. The standard redox potential of these monohydrosilane compounds is approximately −0.4 to 0V. Therefore, the metal ion to be reduced by these monohydrosilane compounds must have a standard redox potential of 0 V or higher. In addition, the standard oxidation-reduction potential of the metal ion produced | generated by ionization from a metal salt can be measured by measuring methods, such as cyclic voltammetry.
金属イオンとは、単数あるいは複数の電子を失った金属原子のことであり、一般に、金属と酸の反応等の化学的な方法や電気分解等の電気的な方法あるいは金属塩を水若しくは有機溶媒に溶解させる方法によって生成される。本実施例においては、金属イオンの供給源として塩化金（ＡｕＣｌ３）等の金塩、塩化白金酸（Ｈ２ＰｔＣｌ６・６Ｈ２Ｏ）等の白金塩、酢酸パラジウム（Ｐｄ（ＣＨ３ＣＯＯ）２）、塩化パラジウム（ＰｄＣｌ２）等のパラジウム塩、酢酸銀（ＣＨ３ＣＯＯＡｇ）、トリフルオロ酢酸銀（ＣＦ３ＣＯＯＡｇ）等の銀塩等を用いている。同様に、塩化白金（ＩＶ）（ＰｔＣｌ４）の白金（ＩＶ）塩、塩化銅（Ｉ）（ＣｕＣｌ）、酢酸銅（Ｃｕ（ＣＨ３ＣＯＯ）２）等の銅塩等を用いることも可能である。
これらの金属塩は溶液中で金属イオンと陰イオンに電離する。そして、金属イオンとして、パラジウムイオン（Ｐｄ２＋）、白金イオン（Ｐｔ２＋、Ｐｔ４＋）、金イオン（Ａｕ３＋）、銅イオン（Ｃｕ＋、Ｃｕ２＋）等が生成される。なお、本願発明に用いる金属イオンは、既に述べたように標準酸化還元電位が０Ｖ以上であり、モノヒドロシラン化合物と還元反応するものであればよく、その元素および価数は本実施例に示す場合に限定されるものではない。
A metal ion is a metal atom that has lost one or more electrons. Generally, a chemical method such as a reaction between a metal and an acid, an electrolysis method such as electrolysis, or a metal salt in water or an organic solvent. It is produced by the method of dissolving in In the present embodiment, gold chloride as a source of metal ions (AuCl 3) a gold salt such as, platinum salts such as chloroplatinic acid (H 2 PtCl 6 · 6H 2 O), palladium acetate (Pd (CH 3 COO) 2 ), palladium salts such as palladium chloride (PdCl 2 ), and silver salts such as silver acetate (CH 3 COOAg) and silver trifluoroacetate (CF 3 COOAg). Similarly, a platinum (IV) salt of platinum (IV) chloride (PtCl 4 ), a copper salt such as copper chloride (I) (CuCl), copper acetate (Cu (CH 3 COO) 2 ), etc. can be used. is there.
These metal salts ionize into metal ions and anions in solution. As metal ions, palladium ions (Pd 2+ ), platinum ions (Pt 2+ , Pt 4+ ), gold ions (Au 3+ ), copper ions (Cu + , Cu 2+ ) and the like are generated. The metal ion used in the present invention may be any metal ion as long as it has a standard oxidation-reduction potential of 0 V or more as described above and can react with the monohydrosilane compound. It is not limited to.
上記金属塩から電離する陰イオンとしては、例えば、水酸化物イオン（ＯＨ−）、酢酸イオン（ＣＨ３ＣＯＯ−）、硝酸イオン（ＮＯ３ −）、トリフルオロ酢酸イオン（ＣＦ３ＣＯＯ−）、塩化物イオン（Ｃｌ−）、臭化物イオン（Ｂｒ−）、フッ化物イオン（Ｆ−）などがあげられる。これらの陰イオンは、多くの場合、モノヒドロシラン化合物と反応して新たな化合物を形成する。例えば、酢酸イオン（ＣＨ３ＣＯＯ−）と金属イオンの溶液にトリメチルシラン（（ＣＨ３）３ＳｉＨ）を加えると、酢酸トリメチルシリル（（ＣＨ３）３ＳｉＣＨ３ＣＯＯ）が生成される。また、塩化物イオン（Ｃｌ−）を含む溶液の場合は、クロロシラン化合物が生成される。なお、酢酸トリメチルシリル（（ＣＨ３）３ＳｉＣＨ３ＣＯＯ）及びクロロシラン化合物は沸点が低く、蒸発し易いという特性を有している。また、陰イオンとしてトリフルオロ酢酸イオン（ＣＦ３ＣＯＯ−）、臭化物イオン（Ｂｒ−）及びヨウ化物イオン（Ｉ−）を用いた場合にも、やはり蒸発し易い特性を有する化合物が生成される。しかし、臭化物イオン（Ｂｒ−）若しくはヨウ化物イオン（Ｉ−）とモノヒドロシラン化合物との反応によって生成されるブロモシラン又はヨードシランは加水分解性が強いため、それらの取扱いは無水状態で行う必要がある。すなわち、製造工程における取扱い等の作業性を考慮すると、酢酸イオン（ＣＨ３ＣＯＯ−）、トリフルオロ酢酸イオン（ＣＦ３ＣＯＯ−）又は塩化物イオン（Ｃｌ−）、フッ化物イオン（Ｆ−）を陰イオンとして含む金属塩を使用することが望ましい。この場合、モノヒドロシラン化合物と陰イオンとの反応により生成されるケイ素化合物は比較的安定なものとなるため、製造環境を厳密な無水条件に設定する必要がない。従って、乾燥設備の設置等による余分な設備費用は発生しない。 Examples of the anion ionized from the metal salt include hydroxide ion (OH − ), acetate ion (CH 3 COO − ), nitrate ion (NO 3 − ), trifluoroacetate ion (CF 3 COO − ), Examples include chloride ion (Cl − ), bromide ion (Br − ), fluoride ion (F − ), and the like. These anions often react with monohydrosilane compounds to form new compounds. For example, when trimethylsilane ((CH 3 ) 3 SiH) is added to a solution of acetate ions (CH 3 COO − ) and metal ions, trimethylsilyl acetate ((CH 3 ) 3 SiCH 3 COO) is generated. In the case of a solution containing chloride ions (Cl − ), a chlorosilane compound is generated. Note that trimethylsilyl acetate ((CH 3 ) 3 SiCH 3 COO) and a chlorosilane compound have a low boiling point and are easily evaporated. In addition, when trifluoroacetate ion (CF 3 COO − ), bromide ion (Br − ) and iodide ion (I − ) are used as anions, a compound having a characteristic that is easily evaporated is also produced. However, since bromosilane or iodosilane produced by the reaction of bromide ion (Br − ) or iodide ion (I − ) with a monohydrosilane compound is highly hydrolyzable, it is necessary to handle them in an anhydrous state. That is, in consideration of workability such as handling in the manufacturing process, acetate ion (CH 3 COO − ), trifluoroacetate ion (CF 3 COO − ), chloride ion (Cl − ), fluoride ion (F − ) It is desirable to use a metal salt containing as an anion. In this case, since the silicon compound produced by the reaction between the monohydrosilane compound and the anion becomes relatively stable, it is not necessary to set the production environment under strict anhydrous conditions. Therefore, there is no extra equipment cost due to the installation of drying equipment.
なお、金属イオンとモノヒドロシラン化合物を反応させる際には、溶媒や添加剤等を共存させても良い。溶媒としては、例えば、メタノール、エタノール、１−プロパノール、２−プロパノール、ブタノール、ｓｅｃ−ブタノール、ｔｅｒｔ−ブタノール、エチレングリコール、プロピレングリコール、フェノール、シクロへキサノール等のアルコール類、ジエチルエーテル、ジイソプロピルエーテル、ジブチルエーテル、テトラヒドロフラン、２−メチルテトラヒドロフラン、ジオキサン等のエーテル類、ペンタン、ヘキサン、ヘプタン、オクタン、ノナン、デカン、ウンデカン、ドデカン、トリデカン、テトラデカン、シクロヘキサン、ベンゼン、トルエン、キシレン、メシチレン、ビニルベンゼン、フェニルアセチレン、トラン等の炭化水素類、フルオロベンゼンクロロベンゼン、クロロホルム、ジクロロメタン、ブロモベンゼン、ヨードベンゼン等のハロゲン化炭化水素類、トリエチルアミン、アニリン、ピリジン等のアミン類、アセトン、シクロヘキサノン、アセトフェノン等のケトン類、酢酸エチル、酢酸イソプロピル、安息香酸メチル、γ―ブチロラクトン、エチレンカーボート、プロピレンカーボネート等のエステル類等、Ｎ−メチル−２−ピロリドン、アセトアニリド等のアミド類、ベンゾニトリル、４−シアノ−４’−ペンチルビフェニル、４−シアノ−４’−ペンチルオキシビフェニル、等のニトリル化合物類、ニトロベンゼン等のニトロ化合物類、ヘキサンチオール、ヘプタンチオール、オクタンチオール等のチオール類および水等の溶媒から単独あるいは混合して用いることができる。また、カルボン酸塩、アルキルスルホン酸塩等の界面活性剤類、ポリ（Ｎ−ビニルピロリドン）、オレイン酸等のカルボン酸類等の酸類、ポリアクリル酸、ポリエチレングリコール、ポリ（ジメチルシロキサン）等の高分子類を添加しても良い。なお、本願発明で使用可能な溶媒は本実施例に示すものに限定されるものではない。すなわち、モノヒドロシラン化合物による金属イオンの還元反応を阻害しないものであれば、上記溶媒以外の溶媒であっても良い。 In addition, when making a metal ion and a monohydrosilane compound react, you may coexist a solvent, an additive, etc. Examples of the solvent include methanol, ethanol, 1-propanol, 2-propanol, butanol, sec-butanol, tert-butanol, alcohols such as ethylene glycol, propylene glycol, phenol, cyclohexanol, diethyl ether, diisopropyl ether, Ethers such as dibutyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, dioxane, pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, tridecane, tetradecane, cyclohexane, benzene, toluene, xylene, mesitylene, vinylbenzene, phenyl Hydrocarbons such as acetylene and tolane, fluorobenzene chlorobenzene, chloroform, dichloromethane, bromobenzene, iodo Halogenated hydrocarbons such as benzene, amines such as triethylamine, aniline, pyridine, ketones such as acetone, cyclohexanone, acetophenone, ethyl acetate, isopropyl acetate, methyl benzoate, γ-butyrolactone, ethylene carboat, propylene carbonate, etc. Esters such as N-methyl-2-pyrrolidone, amides such as acetanilide, nitrile compounds such as benzonitrile, 4-cyano-4′-pentylbiphenyl, 4-cyano-4′-pentyloxybiphenyl, nitrobenzene Nitro compounds such as hexanethiol, heptanethiol, octanethiol and the like, and solvents such as water can be used alone or in combination. Also, surfactants such as carboxylates and alkyl sulfonates, acids such as poly (N-vinylpyrrolidone) and carboxylic acids such as oleic acid, polyacrylic acid, polyethylene glycol, poly (dimethylsiloxane) Molecules may be added. In addition, the solvent which can be used by this invention is not limited to what is shown in a present Example. That is, a solvent other than the above solvent may be used as long as it does not inhibit the reduction reaction of metal ions by the monohydrosilane compound.
金属イオンとモノヒドロシラン化合物を反応させる際に溶媒を用いる場合、反応温度は、溶媒の還流温度以下であることが望ましい。ただし、これに限定されるものではなく、溶媒の沸点以上とすることもできる。また、金属イオンとモノヒドロシラン化合物とを、溶媒を蒸発させながら反応させても良い。なお、金属イオンとモノヒドロシラン化合物とを反応させる際には、反応を均一に進行させる必要があるため、磁気攪拌子やスリーワンモーター等の攪拌機で溶液を攪拌することが好ましい。また、撹拌機は、得られる金属ナノ粒子の均一性を高めるため、せん断速度が０．５ｍ／秒以上となるように設定することが望ましい。 When using a solvent when reacting a metal ion and a monohydrosilane compound, the reaction temperature is preferably not higher than the reflux temperature of the solvent. However, it is not limited to this, It can also be made more than the boiling point of a solvent. Further, the metal ion and the monohydrosilane compound may be reacted while the solvent is evaporated. In addition, when reacting a metal ion and a monohydrosilane compound, since it is necessary to advance reaction uniformly, it is preferable to stir a solution with stirrers, such as a magnetic stirrer and a three-one motor. The stirrer is preferably set so that the shear rate is 0.5 m / second or more in order to improve the uniformity of the metal nanoparticles obtained.
金属イオンとモノヒドロシラン化合物との反応時間は、反応温度や溶媒等により異なるが、反応の終点についてはイオンクロマトグラフィー等で残留する金属イオンを定量することで調べることができる。なお、反応の終点は、生成される金属ナノ粒子と原料の金属イオンとで可視−紫外領域の吸収スペクトルが異なるという現象を利用することによっても調べることができる。
また、金属イオンとモノヒドロシラン化合物を反応させるときの圧力は、特に限定されるものではないが、少なくとも反応に使用する容器の耐圧限界以下で行う必要がある。
The reaction time between the metal ion and the monohydrosilane compound varies depending on the reaction temperature, the solvent, and the like, but the end point of the reaction can be examined by quantifying the remaining metal ion by ion chromatography or the like. The end point of the reaction can also be examined by utilizing the phenomenon that the absorption spectrum in the visible-ultraviolet region is different between the produced metal nanoparticles and the raw material metal ions.
Moreover, the pressure at the time of making a metal ion and a monohydrosilane compound react is although it does not specifically limit, It is necessary to carry out below the pressure | voltage limit of the container used for reaction at least.
金属イオンとモノヒドロシラン化合物との反応濃度は特に限定されるものではなく、適宜変更可能である。すなわち、金属ナノ粒子の用途に応じて、懸濁液中の金属含有量が所望の値となるように、溶媒等の添加や濃縮等で反応濃度を調整すると良い。例えば、金属ナノ粒子を液晶に添加する場合には、懸濁液中の金属含有量が１００ｐｐｍ以上１０％未満となるように反応濃度を設定し、また、金属ナノ粒子を配線材料として利用する場合には、懸濁液中の金属含有量が５％以上９５％未満となるように反応濃度を設定することが望ましい。
なお、金属イオンに対するモノヒドロシラン化合物の添加量が少ない場合には、生成された懸濁液中の金属イオン濃度が低くなるため、本実施例においてはモノヒドロシラン化合物の添加量を金属イオンが完全に金属に還元される理論値の１乃至１０倍に設定している。
The reaction concentration between the metal ion and the monohydrosilane compound is not particularly limited and can be changed as appropriate. That is, according to the use of the metal nanoparticles, the reaction concentration may be adjusted by adding or concentrating a solvent or the like so that the metal content in the suspension becomes a desired value. For example, when adding metal nanoparticles to the liquid crystal, the reaction concentration is set so that the metal content in the suspension is 100 ppm or more and less than 10%, and the metal nanoparticles are used as a wiring material. It is desirable to set the reaction concentration so that the metal content in the suspension is 5% or more and less than 95%.
Note that when the amount of the monohydrosilane compound added to the metal ions is small, the concentration of the metal ion in the generated suspension becomes low. Therefore, in this example, the amount of the monohydrosilane compound added is completely reduced. It is set to 1 to 10 times the theoretical value reduced to metal.
上記方法によって製造した金属ナノ粒子の懸濁液は、還元剤であるモノヒドロシラン化合物に由来するケイ素化合物が含まれている。例えば、酢酸銀（ＣＨ３ＣＯＯＡｇ）とトリエチルシラン（（Ｃ２Ｈ５）３ＳｉＨ）の反応では、酢酸トリエチルシリル（（Ｃ２Ｈ５）３ＳｉＣＨ３ＣＯＯ）が生成される。このように、還元反応後に生成されるケイ素化合物は、とくに不都合がなければ取り除く必要はないが、一般には金属ナノ粒子の高純度化のため、分離・除去する必要がある。
本実施例で示した方法によって生成されるケイ素化合物は沸点が低く、蒸発し易いという特性を有している。また、還元剤として使用されるモノヒドロシラン化合物自体も蒸発し易い物質である。すなわち、本願発明の金属ナノ粒子の製造方法においては、金属ナノ粒子の懸濁液中に残留する有機ケイ素化合物や余剰還元剤などの夾雑物が蒸発によって容易に除去され得るという作用を有する。
なお、これらの夾雑物を蒸発させる際の条件は、とくに限定されるものではないが、例えば、気圧は１０１３ｈPa以下とし、温度は０℃以上１５０℃以下にすると良い。ただし、金属ナノ粒子を高温に曝すと焼結が進行するため、温度については０℃以上１００℃以下とすることがより好ましい。
The suspension of metal nanoparticles produced by the above method contains a silicon compound derived from a monohydrosilane compound that is a reducing agent. For example, in the reaction of silver acetate (CH 3 COOAg) and triethylsilane ((C 2 H 5 ) 3 SiH), triethylsilyl acetate ((C 2 H 5 ) 3 SiCH 3 COO) is generated. As described above, the silicon compound produced after the reduction reaction does not need to be removed unless particularly inconvenient, but generally needs to be separated and removed in order to increase the purity of the metal nanoparticles.
The silicon compound produced by the method shown in this example has a low boiling point and is easy to evaporate. In addition, the monohydrosilane compound itself used as a reducing agent is a substance that easily evaporates. That is, the metal nanoparticle production method of the present invention has an effect that impurities such as an organosilicon compound and an excess reducing agent remaining in the suspension of metal nanoparticles can be easily removed by evaporation.
The conditions for evaporating these impurities are not particularly limited. For example, the atmospheric pressure may be 1013 hPa or less, and the temperature may be 0 ° C. or more and 150 ° C. or less. However, since sintering proceeds when the metal nanoparticles are exposed to a high temperature, the temperature is more preferably 0 ° C. or more and 100 ° C. or less.
以上説明したように、本実施例の製造方法によれば、金属ナノ粒子を製造する過程でモノヒドロシラン化合物と金属塩の陰イオンの反応によって生成されるケイ素化合物及び懸濁液中に残留する余剰還元剤を蒸発により安全かつ効率よく除去することが可能である。これにより、懸濁液中の金属ナノ粒子の純度を効率よく高めることができる。そして、このように懸濁液中の夾雑物を蒸発によって除去することによれば、高価な設備が不要であるため、設備コストの削減を図ることができる。従って、金属ナノ粒子を安価に製造することが可能である。 As described above, according to the manufacturing method of this example, the silicon compound produced by the reaction of the anion of the monohydrosilane compound and the metal salt in the process of manufacturing the metal nanoparticles and the surplus remaining in the suspension It is possible to remove the reducing agent safely and efficiently by evaporation. Thereby, the purity of the metal nanoparticles in the suspension can be increased efficiently. And by removing the impurities in the suspension in this way by evaporation, expensive equipment is not necessary, so that equipment costs can be reduced. Therefore, it is possible to produce metal nanoparticles at a low cost.
次に、本願発明について具体的に実施例を挙げて説明する。なお、各実施例においては、金属ナノ粒子の粒径をＸ線小角散乱法により測定した。また、１Ｈ−ＮＭＲスペクトルの測定により、ケイ素由来の化合物を検出した。 Next, the present invention will be described with specific examples. In each example, the particle size of the metal nanoparticles was measured by the X-ray small angle scattering method. Moreover, the compound derived from silicon was detected by the measurement of < 1 > H-NMR spectrum.
（実施例１）
エチレングリコール（ＨＯＣＨ２ＣＨ２ＯＨ）１０ｇ、オクチルアミン（Ｃ８Ｈ１７ＮＨ２）３．０ｇ、酢酸銀（ＣＨ３ＣＯＯＡｇ）１．０ｇの混合物に攪拌しながらトリエチルシラン（（Ｃ２Ｈ５）３ＳｉＨ）０．７ｇを加えて室温で１時間攪拌することで、褐色の銀ナノ粒子の懸濁液を得た。このとき、銀ナノ粒子の平均粒径は３．５ｎｍであった。
本実施例は、一般式（１）で示されるヒドロシラン化合物に該当するトリエチルシラン（（Ｃ２Ｈ５）３ＳｉＨ）を還元剤として使用することで、銀ナノ粒子が生成されたことを示している。
Example 1
While stirring a mixture of ethylene glycol (HOCH 2 CH 2 OH) 10 g, octylamine (C 8 H 17 NH 2 ) 3.0 g, and silver acetate (CH 3 COOAg) 1.0 g, triethylsilane ((C 2 H 5 )) 3 SiH) 0.7 g was added and stirred at room temperature for 1 hour to obtain a suspension of brown silver nanoparticles. At this time, the average particle diameter of the silver nanoparticles was 3.5 nm.
This example shows that silver nanoparticles were generated by using triethylsilane ((C 2 H 5 ) 3 SiH) corresponding to the hydrosilane compound represented by the general formula (1) as a reducing agent. Yes.
（実施例２）
水５０ｇにポリ（Ｎ−ビニルピロリドン）２．０ｇ、酢酸銀（ＣＨ３ＣＯＯＡｇ）０．２gを溶解し、攪拌しながらトリエチルシラン（（Ｃ２Ｈ５）３ＳｉＨ）０．２ｇを加えて室温で１時間攪拌することで、黄褐色の銀ナノ粒子の懸濁液を得た。このとき、銀ナノ粒子の平均粒径は７．４ｎｍであった。
本実施例においても、トリエチルシラン（（Ｃ２Ｈ５）３ＳｉＨ）を還元剤として使用しており、銀ナノ粒子が確かに生成されている。
(Example 2)
In 50 g of water, 2.0 g of poly (N-vinylpyrrolidone) and 0.2 g of silver acetate (CH 3 COOAg) are dissolved, and 0.2 g of triethylsilane ((C 2 H 5 ) 3 SiH) is added with stirring to room temperature. Was stirred for 1 hour to obtain a suspension of yellow-brown silver nanoparticles. At this time, the average particle diameter of the silver nanoparticles was 7.4 nm.
Also in this example, triethylsilane ((C 2 H 5 ) 3 SiH) is used as a reducing agent, and silver nanoparticles are certainly generated.
（実施例３）
トルエン（Ｃ６Ｈ５ＣＨ３）１０ｇ、オクチルアミン（Ｃ８Ｈ１７ＮＨ２）１．５ｇ、酢酸銀（ＣＨ３ＣＯＯＡｇ）０．５ｇの混合物に攪拌しながらトリエチルシラン（（Ｃ２Ｈ５）３ＳｉＨ）０．４ｇを加えて室温で１時間攪拌することで、褐色の銀ナノ粒子の懸濁液を得た。このとき、銀ナノ粒子の平均粒径は３．８ｎｍであった。さらに、エバポレータで濃縮すると銀ナノ粒子が黒褐色の固体として得られた。得られた固体を重水素化溶媒に分散させて１Ｈ−ＮＭＲスペクトルを測定すると、ケイ素由来の化合物は含まれていないことがわかった。なお、エバポレータとは、固体または液体を減圧して蒸発させる機能をもつ装置である。
本実施例は、トリエチルシラン（（Ｃ２Ｈ５）３ＳｉＨ）を還元剤として使用することで、銀ナノ粒子が生成されるとともに、蒸発により夾雑物が除去されたことを示している。
(Example 3)
While stirring a mixture of 10 g of toluene (C 6 H 5 CH 3 ), 1.5 g of octylamine (C 8 H 17 NH 2 ) and 0.5 g of silver acetate (CH 3 COOAg), triethylsilane ((C 2 H 5 ) 3 SiH) 0.4 g was added and stirred at room temperature for 1 hour to obtain a suspension of brown silver nanoparticles. At this time, the average particle diameter of the silver nanoparticles was 3.8 nm. Further, when concentrated with an evaporator, silver nanoparticles were obtained as a black-brown solid. When the obtained solid was dispersed in a deuterated solvent and measured for 1 H-NMR spectrum, it was found that no silicon-derived compound was contained. An evaporator is a device having a function of depressurizing and evaporating a solid or liquid.
This example shows that by using triethylsilane ((C 2 H 5 ) 3 SiH) as a reducing agent, silver nanoparticles were generated and impurities were removed by evaporation.
（実施例４）
トルエン（Ｃ６Ｈ５ＣＨ３）１０ｇ、オクタンチオール（ＣＨ３（ＣＨ２）７ＳＨ）２ｇ、塩化金（ＡｕＣｌ３）０．１ｇの混合物に攪拌しながらトリエチルシラン（（Ｃ２Ｈ５）３ＳｉＨ）０．４ｇを加えて室温で１時間攪拌することで、暗赤色の金ナノ粒子の懸濁液を得た。このとき、金ナノ粒子の平均粒径は３．８ｎｍであった。
本実施例は、トリエチルシラン（（Ｃ２Ｈ５）３ＳｉＨ）を還元剤として使用することで、金ナノ粒子が生成されたことを示している。
Example 4
While stirring a mixture of 10 g of toluene (C 6 H 5 CH 3 ), 2 g of octanethiol (CH 3 (CH 2 ) 7 SH) and 0.1 g of gold chloride (AuCl 3 ), triethylsilane ((C 2 H 5 ) 3 0.4 g of SiH) was added and stirred at room temperature for 1 hour to obtain a suspension of dark red gold nanoparticles. At this time, the average particle diameter of the gold nanoparticles was 3.8 nm.
This example shows that gold nanoparticles were generated by using triethylsilane ((C 2 H 5 ) 3 SiH) as a reducing agent.
（実施例５）
水５０ｇにポリ（Ｎ−ビニルピロリドン）２．０ｇ、酢酸パラジウム（Ｐｄ（ＣＨ３ＣＯＯ）２）０．２gを溶解し、攪拌しながらトリエチルシラン（（Ｃ２Ｈ５）３ＳｉＨ）０．４ｇを加えて室温で１時間攪拌することで、暗褐色のパラジウムナノ粒子の懸濁液を得た。このとき、パラジウムナノ粒子の平均粒径は１３．２ｎｍであった。
本実施例は、トリエチルシラン（（Ｃ２Ｈ５）３ＳｉＨ）を還元剤として使用することで、パラジウムナノ粒子が生成されたことを示している。
(Example 5)
In 50 g of water, 2.0 g of poly (N-vinylpyrrolidone) and 0.2 g of palladium acetate (Pd (CH 3 COO) 2 ) are dissolved, and 0.4 g of triethylsilane ((C 2 H 5 ) 3 SiH) is stirred. Was added and stirred at room temperature for 1 hour to obtain a suspension of dark brown palladium nanoparticles. At this time, the average particle diameter of the palladium nanoparticles was 13.2 nm.
This example shows that palladium nanoparticles were produced by using triethylsilane ((C 2 H 5 ) 3 SiH) as a reducing agent.
（実施例６）
水５０ｇにポリ（Ｎ−ビニルピロリドン）２．０ｇ、塩化白金酸（Ｈ２ＰｔＣｌ６・６Ｈ２Ｏ）０．１gを溶解し、攪拌しながらトリエチルシラン（（Ｃ２Ｈ５）３ＳｉＨ）０．５ｇを加えて室温で１時間攪拌することで、黒色の白金ナノ粒子の懸濁液を得た。このとき、白金ナノ粒子の平均粒径は７．９ｎｍであった。
本実施例においても、トリエチルシラン（（Ｃ２Ｈ５）３ＳｉＨ）を還元剤として使用しており、白金ナノ粒子が確かに生成されている。
(Example 6)
Water 50g poly (N- vinylpyrrolidone) 2.0 g, was dissolved chloroplatinic acid (H 2 PtCl 6 · 6H 2 O) 0.1g, stirring triethylsilane ((C 2 H 5) 3 SiH) 0 0.5 g was added and stirred at room temperature for 1 hour to obtain a suspension of black platinum nanoparticles. At this time, the average particle diameter of the platinum nanoparticles was 7.9 nm.
Also in this example, triethylsilane ((C 2 H 5 ) 3 SiH) is used as a reducing agent, and platinum nanoparticles are certainly generated.
（実施例７）
テトラヒドロフラン（Ｃ４Ｈ８Ｏ）４４ｇに４−シアノ−４’−ペンチルビフェニルを４１ｍｇ、酢酸銀（ＣＨ３ＣＯＯＡｇ）３ｍｇ、酢酸パラジウム（Ｐｄ（ＣＨ３ＣＯＯ）２）４ｍｇ加えて溶解し、トリエチルシラン（（Ｃ２Ｈ５）３ＳｉＨ）１０ｍｇを加えて攪拌することで、銀／パラジウムナノ粒子の懸濁液を得た。このとき、銀／パラジウムナノ粒子の平均粒径は６．５ｎｍであった。
本実施例は、トリエチルシラン（（Ｃ２Ｈ５）３ＳｉＨ）を還元剤として使用することで、銀／パラジウムナノ粒子が生成されたことを示している。
(Example 7)
To 44 g of tetrahydrofuran (C 4 H 8 O), 41 mg of 4-cyano-4′-pentylbiphenyl, 3 mg of silver acetate (CH 3 COOAg) and 4 mg of palladium acetate (Pd (CH 3 COO) 2 ) were added and dissolved, and triethylsilane A suspension of silver / palladium nanoparticles was obtained by adding 10 mg of ((C 2 H 5 ) 3 SiH) and stirring. At this time, the average particle diameter of the silver / palladium nanoparticles was 6.5 nm.
This example shows that silver / palladium nanoparticles were produced by using triethylsilane ((C 2 H 5 ) 3 SiH) as a reducing agent.
（実施例８）
エチレングリコール（ＨＯＣＨ２ＣＨ２ＯＨ）１０ｇ、オクチルアミン（Ｃ８Ｈ１７ＮＨ２）３．０ｇ、酢酸銀（ＣＨ３ＣＯＯＡｇ）１．０ｇの混合物に攪拌しながらデシルジメチルシラン（Ｃ１０Ｈ２１（ＣＨ３）２ＳｉＨ）０．７ｇを加えて室温で１時間攪拌することで、褐色の銀ナノ粒子の懸濁液を得た。このとき、銀ナノ粒子の平均粒径は３．５ｎｍであった。
本実施例は、一般式（１）で示されるヒドロシラン化合物に該当するデシルジメチルシラン（Ｃ１０Ｈ２１（ＣＨ３）２ＳｉＨ）を還元剤として使用することで、銀ナノ粒子が生成されたことを示している。
(Example 8)
While stirring a mixture of 10 g of ethylene glycol (HOCH 2 CH 2 OH), 3.0 g of octylamine (C 8 H 17 NH 2 ) and 1.0 g of silver acetate (CH 3 COOAg), decyldimethylsilane (C 10 H 21 ( A suspension of brown silver nanoparticles was obtained by adding 0.7 g of CH 3 ) 2 SiH) and stirring at room temperature for 1 hour. At this time, the average particle diameter of the silver nanoparticles was 3.5 nm.
In this example, silver nanoparticles were generated by using decyldimethylsilane (C 10 H 21 (CH 3 ) 2 SiH) corresponding to the hydrosilane compound represented by the general formula (1) as a reducing agent. Is shown.
（比較例１）
エチレングリコール（ＨＯＣＨ２ＣＨ２ＯＨ）１０ｇ、オクチルアミン（Ｃ８Ｈ１７ＮＨ２）３．０ｇ、酢酸銀（ＣＨ３ＣＯＯＡｇ）１．０ｇの混合物にフェニルシラン（Ｃ６Ｈ５ＳｉＨ３）０．３ｇを加えて室温で１時間攪拌したところ、黒色の銀が沈殿するのみで分散液は得られなかった。
フェニルシラン（Ｃ６Ｈ５ＳｉＨ３）はベンゼン環を有しており、一般式（１）で示されるモノヒドロシラン化合物に該当しない。すなわち、本実施例は、モノヒドロシラン化合物であっても一般式（１）で示される構造を有していないため、銀ナノ粒子が生成されないことを示している。
(Comparative Example 1)
A mixture of 10 g of ethylene glycol (HOCH 2 CH 2 OH), 3.0 g of octylamine (C 8 H 17 NH 2 ), 1.0 g of silver acetate (CH 3 COOAg) and phenylsilane (C 6 H 5 SiH 3 ) 0. When 3 g was added and stirred at room temperature for 1 hour, black silver was only precipitated and no dispersion was obtained.
Phenylsilane (C 6 H 5 SiH 3 ) has a benzene ring and does not correspond to the monohydrosilane compound represented by the general formula (1). That is, this example shows that silver nanoparticles are not generated because the monohydrosilane compound does not have the structure represented by the general formula (1).
（比較例２）
エチレングリコール（ＨＯＣＨ２ＣＨ２ＯＨ）１０ｇ、オクチルアミン（Ｃ８Ｈ１７ＮＨ２）３．０ｇ、酢酸銀（ＣＨ３ＣＯＯＡｇ）１．０ｇの混合物にフェニルメチルシラン（Ｃ６Ｈ５ＣＨ３ＳｉＨ２）０．５ｇを加えて室温で１時間攪拌したところ、黒色の銀が沈殿するのみで分散液は得られなかった。
フェニルメチルシラン（Ｃ６Ｈ５ＣＨ３ＳｉＨ２）もベンゼン環を有しており、一般式（１）で示されるモノヒドロシラン化合物に該当しないことから、本実施例においても、銀ナノ粒子が生成されないことが分かる。
(Comparative Example 2)
To a mixture of 10 g of ethylene glycol (HOCH 2 CH 2 OH), 3.0 g of octylamine (C 8 H 17 NH 2 ) and 1.0 g of silver acetate (CH 3 COOAg), phenylmethylsilane (C 6 H 5 CH 3 SiH 2 ) When 0.5 g was added and stirred at room temperature for 1 hour, black silver only precipitated and no dispersion was obtained.
Since phenylmethylsilane (C 6 H 5 CH 3 SiH 2 ) also has a benzene ring and does not correspond to the monohydrosilane compound represented by the general formula (1), silver nanoparticles are also produced in this example. I understand that it is not done.
（比較例３）
トルエン（Ｃ６Ｈ５ＣＨ３）１０ｇ、オクチルアミン（Ｃ８Ｈ１７ＮＨ２）１．５ｇ、酢酸銀（ＣＨ３ＣＯＯＡｇ）０．５ｇの混合物にドデシルジメチルシラン（Ｃ１２Ｈ２５（ＣＨ３）２ＳｉＨ）０．９ｇを加えて室温で１時間攪拌することで、褐色の銀ナノ粒子の懸濁液を得た。このとき、銀ナノ粒子の平均粒径は４．５ｎｍであった。さらに、エバポレータで濃縮すると銀ナノ粒子が黒褐色の固体として得られた。得られた固体を重水素化溶媒に分散させて１Ｈ−ＮＭＲスペクトルを測定するとドデシルジメチルシラン（Ｃ１２Ｈ２５（ＣＨ３）２ＳｉＨ）由来のピークを確認した。
ドデシルジメチルシラン（Ｃ１２Ｈ２５（ＣＨ３）２ＳｉＨ）は有機基の炭素数の合計が１２よりも多いため、蒸発し難いという特性を有する。従って、本実施例に示すように、銀イオンの還元により銀ナノ粒子は生成されるものの、余剰還元剤が蒸発せずに懸濁液中に残留することになる。
(Comparative Example 3)
To a mixture of 10 g of toluene (C 6 H 5 CH 3 ), 1.5 g of octylamine (C 8 H 17 NH 2 ), and 0.5 g of silver acetate (CH 3 COOAg), dodecyldimethylsilane (C 12 H 25 (CH 3 )) 2 SiH) 0.9 g was added and stirred at room temperature for 1 hour to obtain a suspension of brown silver nanoparticles. At this time, the average particle diameter of the silver nanoparticles was 4.5 nm. Further, when concentrated with an evaporator, silver nanoparticles were obtained as a black-brown solid. When the obtained solid was dispersed in a deuterated solvent and measured for 1 H-NMR spectrum, a peak derived from dodecyldimethylsilane (C 12 H 25 (CH 3 ) 2 SiH) was confirmed.
Since dodecyldimethylsilane (C 12 H 25 (CH 3 ) 2 SiH) has more than 12 carbon atoms in the organic group, it has a characteristic that it is difficult to evaporate. Therefore, as shown in the present Example, although silver nanoparticles are produced by reduction of silver ions, the surplus reducing agent does not evaporate and remains in the suspension.
請求項１乃至請求項３に記載された発明は、電子部品の配線材料や液晶表示装置等、各種分野で使用される金属ナノ粒子に対して適用可能である。
The inventions described in claims 1 to 3 are applicable to metal nanoparticles used in various fields such as wiring materials for electronic parts and liquid crystal display devices.
Claims (3)
The metal ion is generated by ionization from a metal salt, and the anion ionized together with the metal ion from the metal salt is at least one selected from acetate ion, trifluoroacetate ion, chloride ion, and fluoride ion. The method for producing metal nanoparticles according to claim 1 or 2, wherein:
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| JP2011157623A (en) * | 2010-01-07 | 2011-08-18 | Tokyo Metropolitan Univ | Metal colloid, method for production thereof and use thereof |
| JP2013147713A (en) * | 2012-01-20 | 2013-08-01 | Nippon Atomized Metal Powers Corp | Method for producing metal nanoparticle, and conductive material |
| JP2013174011A (en) * | 2012-02-24 | 2013-09-05 | Xerox Corp | Process for producing palladium nanoparticle ink |
| JP2014152390A (en) * | 2013-02-13 | 2014-08-25 | Nagoya Univ | Low temperature production method for nanofluid |
| KR101472634B1 (en) * | 2012-10-29 | 2014-12-15 | 삼성전기주식회사 | Metal nano particle, and method for surface treating the same |
| WO2016049430A1 (en) * | 2014-09-26 | 2016-03-31 | The Regents Of The University Of California | Methods to produce ultra-thin metal nanowires for transparent conductors |
| KR20160051341A (en) * | 2014-11-03 | 2016-05-11 | 금오공과대학교 산학협력단 | Process for preparing gold nanoparticles |
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| JPH053343B2 (en) * | 1985-12-19 | 1993-01-14 | Gen Electric | |
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| JP2011157623A (en) * | 2010-01-07 | 2011-08-18 | Tokyo Metropolitan Univ | Metal colloid, method for production thereof and use thereof |
| JP2013147713A (en) * | 2012-01-20 | 2013-08-01 | Nippon Atomized Metal Powers Corp | Method for producing metal nanoparticle, and conductive material |
| JP2013174011A (en) * | 2012-02-24 | 2013-09-05 | Xerox Corp | Process for producing palladium nanoparticle ink |
| EP2913127A4 (en) * | 2012-10-24 | 2016-08-10 | Nippon Soda Co | Production method for particles of element having standard electrode potential greater than 0v |
| US9928945B2 (en) | 2012-10-24 | 2018-03-27 | Nippon Soda Co., Ltd. | Production method for particles of element having standard electrode potential greater than 0V |
| KR101472634B1 (en) * | 2012-10-29 | 2014-12-15 | 삼성전기주식회사 | Metal nano particle, and method for surface treating the same |
| JP2014152390A (en) * | 2013-02-13 | 2014-08-25 | Nagoya Univ | Low temperature production method for nanofluid |
| TWI583799B (en) * | 2014-09-26 | 2017-05-21 | 美國加利福尼亞大學董事會 | Methods to produce ultra-thin metal nanowires for transparent conductors |
| JP2017534755A (en) * | 2014-09-26 | 2017-11-24 | ザ リージェンツ オブ ザ ユニバーシティ オブ カリフォルニア | Method for producing ultrafine metal nanowires for transparent conductors |
| WO2016049430A1 (en) * | 2014-09-26 | 2016-03-31 | The Regents Of The University Of California | Methods to produce ultra-thin metal nanowires for transparent conductors |
| US10406602B2 (en) | 2014-09-26 | 2019-09-10 | The Regents Of The University Of California | Methods to produce ultra-thin metal nanowires for transparent conductors |
| KR101673686B1 (en) * | 2014-11-03 | 2016-11-07 | 금오공과대학교 산학협력단 | Process for preparing gold nanoparticles |
| KR20160051341A (en) * | 2014-11-03 | 2016-05-11 | 금오공과대학교 산학협력단 | Process for preparing gold nanoparticles |
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