JP2005264284A - Composite fine particle, manufacturing method therefor, and film using the particle - Google Patents
Composite fine particle, manufacturing method therefor, and film using the particle Download PDFInfo
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- JP2005264284A JP2005264284A JP2004082161A JP2004082161A JP2005264284A JP 2005264284 A JP2005264284 A JP 2005264284A JP 2004082161 A JP2004082161 A JP 2004082161A JP 2004082161 A JP2004082161 A JP 2004082161A JP 2005264284 A JP2005264284 A JP 2005264284A
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- Prior art keywords
- fine particles
- metal
- particles
- coupling agent
- semiconductor
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- 239000010419 fine particle Substances 0.000 title claims abstract description 132
- 239000002131 composite material Substances 0.000 title claims abstract description 50
- 239000002245 particle Substances 0.000 title claims abstract description 31
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 16
- 229910052751 metal Inorganic materials 0.000 claims abstract description 66
- 239000002184 metal Substances 0.000 claims abstract description 66
- 239000004065 semiconductor Substances 0.000 claims abstract description 55
- 239000007822 coupling agent Substances 0.000 claims abstract description 36
- 239000012212 insulator Substances 0.000 claims abstract description 32
- 239000011882 ultra-fine particle Substances 0.000 claims abstract description 32
- 239000006185 dispersion Substances 0.000 claims abstract description 20
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 12
- 150000003839 salts Chemical class 0.000 claims abstract description 12
- 150000001875 compounds Chemical class 0.000 claims description 28
- 239000002923 metal particle Substances 0.000 claims description 18
- 125000000962 organic group Chemical group 0.000 claims description 7
- 230000009257 reactivity Effects 0.000 claims description 4
- 239000012528 membrane Substances 0.000 claims 2
- 230000000737 periodic effect Effects 0.000 description 21
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 16
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 15
- -1 optical mirrors Substances 0.000 description 14
- 239000010409 thin film Substances 0.000 description 13
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 12
- 239000010408 film Substances 0.000 description 11
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 8
- 239000010931 gold Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 239000000377 silicon dioxide Substances 0.000 description 8
- 239000000758 substrate Substances 0.000 description 8
- 229910052798 chalcogen Inorganic materials 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- 239000011521 glass Substances 0.000 description 7
- 230000000704 physical effect Effects 0.000 description 7
- 229910052709 silver Inorganic materials 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- 239000010949 copper Substances 0.000 description 6
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 6
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine hydrate Chemical compound O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 6
- XLSMFKSTNGKWQX-UHFFFAOYSA-N hydroxyacetone Chemical compound CC(=O)CO XLSMFKSTNGKWQX-UHFFFAOYSA-N 0.000 description 6
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 5
- 229910010413 TiO 2 Inorganic materials 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
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- 239000000243 solution Substances 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
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- 238000002834 transmittance Methods 0.000 description 5
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 4
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- 125000000217 alkyl group Chemical group 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- 239000011787 zinc oxide Substances 0.000 description 4
- 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
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
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- 238000002441 X-ray diffraction Methods 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
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- 238000010304 firing Methods 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
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- 239000003607 modifier Substances 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 3
- 229910052707 ruthenium Inorganic materials 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
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- UUWJHAWPCRFDHZ-UHFFFAOYSA-N 1-dodecoxydodecane;phosphoric acid Chemical compound OP(O)(O)=O.CCCCCCCCCCCCOCCCCCCCCCCCC UUWJHAWPCRFDHZ-UHFFFAOYSA-N 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
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- 229910052796 boron Inorganic materials 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- UHYPYGJEEGLRJD-UHFFFAOYSA-N cadmium(2+);selenium(2-) Chemical compound [Se-2].[Cd+2] UHYPYGJEEGLRJD-UHFFFAOYSA-N 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
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- 238000006243 chemical reaction Methods 0.000 description 2
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- HKOOXMFOFWEVGF-UHFFFAOYSA-N phenylhydrazine Chemical compound NNC1=CC=CC=C1 HKOOXMFOFWEVGF-UHFFFAOYSA-N 0.000 description 2
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- YBNMDCCMCLUHBL-UHFFFAOYSA-N (2,5-dioxopyrrolidin-1-yl) 4-pyren-1-ylbutanoate Chemical compound C=1C=C(C2=C34)C=CC3=CC=CC4=CC=C2C=1CCCC(=O)ON1C(=O)CCC1=O YBNMDCCMCLUHBL-UHFFFAOYSA-N 0.000 description 1
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- ONBWNNUYXGJKKD-UHFFFAOYSA-N 1,4-bis(2-ethylhexoxy)-1,4-dioxobutane-2-sulfonic acid;sodium Chemical compound [Na].CCCCC(CC)COC(=O)CC(S(O)(=O)=O)C(=O)OCC(CC)CCCC ONBWNNUYXGJKKD-UHFFFAOYSA-N 0.000 description 1
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- METCQKAIPQXACO-UHFFFAOYSA-N 3-(tetramethoxy-$l^{5}-stibanyl)propyl 2-methylprop-2-enoate Chemical compound CO[Sb](OC)(OC)(OC)CCCOC(=O)C(C)=C METCQKAIPQXACO-UHFFFAOYSA-N 0.000 description 1
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Landscapes
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- Powder Metallurgy (AREA)
- Non-Insulated Conductors (AREA)
Abstract
Description
本発明は、複合微粒子およびその製造方法に関し、詳しくは基板上に塗布したときに高い透明性を有する導電性微粒子およびその製造方法に関するものである。 The present invention relates to composite fine particles and a method for producing the same, and more particularly to conductive fine particles having high transparency when applied on a substrate and a method for producing the same.
半導体微粒子は、その紫外線、可視光、赤外線の吸収、発光特性や高屈折率性などの物性と共にその透明性を生かして、反射防止膜、光学ミラー、サンスクリーン化粧品、蛍光材料など多くの用途が検討されている。半導体微粒子を薄膜にする場合には高分子マトリクス（例えば、エポキシ系やアクリル系などの光あるいは熱硬化性樹脂）中にこれを分散することが一般的である。この場合の問題として、酸化亜鉛や酸化チタンなどの半導体結晶の光触媒機能により半導体表面の有機物を酸化還元的に分解するため薄膜の安定性が損なわれることが起こる。これを抑制するために、アルコキシシランを原料としたシリカによる被覆が提案されている（例えば、非特許文献１参照）。この方法では光触媒機能の抑制は可能であるが、導電性を付与することはできない。 Semiconductor fine particles have many uses such as antireflection films, optical mirrors, sunscreen cosmetics, fluorescent materials by taking advantage of their transparency, as well as their physical properties such as absorption of ultraviolet rays, visible light, infrared rays, emission characteristics and high refractive index. It is being considered. When the semiconductor fine particles are made into a thin film, it is common to disperse them in a polymer matrix (for example, epoxy or acrylic light or thermosetting resin). As a problem in this case, the organic catalyst on the semiconductor surface is decomposed in an oxidation-reduction manner by the photocatalytic function of a semiconductor crystal such as zinc oxide or titanium oxide, so that the stability of the thin film is impaired. In order to suppress this, coating with silica using alkoxysilane as a raw material has been proposed (see Non-Patent Document 1, for example). Although this method can suppress the photocatalytic function, it cannot impart conductivity.
半導体微粒子の表面を金属で被覆する技術として、半導体微粒子分散液に金属塩および還元剤を添加し、還元により金属微粒子を形成すること（化学めっき法）が開示されている（例えば、特許文献１、特許文献２、及び非特許文献２参照）。この方法は簡便であるが被覆する金属とコアとなる化合物の組合せが限定され、多くの場合金属微粒子と半導体微粒子の混合物が生成するなどの問題点がある。
また、酸化チタン微粒子分散液に銀塩を添加し、紫外線を照射することにより酸化チタン微粒子内部に発生した電子により銀イオンを還元して酸化チタン微粒子表面に銀超微粒子を形成する技術が公開されている（例えば、非特許文献３参照）。しかしながらこの方法もコアになる微粒子が光半導体にしか適用できない、また、銀超微粒子の形成に時間がかかるという問題がある。さらにこの技術をコアが蛍光体である微粒子に適用すると消光する場合があるので改善が要望される。
As a technique for coating the surface of semiconductor fine particles with metal, a method of adding metal salt and a reducing agent to a semiconductor fine particle dispersion and forming metal fine particles by reduction (chemical plating method) is disclosed (for example, Patent Document 1). , Patent Document 2 and Non-Patent Document 2). This method is simple, but the combination of the metal to be coated and the compound serving as the core is limited. In many cases, there is a problem that a mixture of metal fine particles and semiconductor fine particles is formed.
In addition, a technology for forming silver ultrafine particles on the surface of titanium oxide fine particles by reducing silver ions with electrons generated inside the titanium oxide fine particles by adding silver salt to the titanium oxide fine particle dispersion and irradiating ultraviolet rays is disclosed. (For example, refer nonpatent literature 3). However, this method also has a problem that the core fine particles can be applied only to an optical semiconductor, and it takes time to form silver ultrafine particles. Furthermore, if this technique is applied to fine particles whose core is a phosphor, quenching may occur, and improvements are desired.
一方、絶縁体微粒子は、ポリメチルメタクリレート、ポリスチレン、ポリカーボネート、ポリエチレンテレフタレート、ポリオレフィンなどの有機物、シリカ、アルミナなどの無機物があり、比較的屈折率や比重が小さいという物性面での特徴を有する。これに導電性が付与できれば薄膜にした場合、透明性を保持したまま帯電による汚染などが防止されるので望ましい。また、分散液で用いる場合には比重が小さいので貴金属を表面に被覆しても沈降しにくいという長所がある。しかし、従来、透明性を確保しつつ絶縁体微粒子に十分な導電性を付与することはできなかった。
従って、本発明の目的は、多くの半導体又は絶縁体の表面に金属超微粒子を結合した複合微粒子、特に透明性の高い導電性微粒子およびその製造方法を提供することである。
また、簡易且つ迅速な上記複合微粒子の製造方法を提供することである。
本発明は、さらに、コアの化合物の物性を保持し、且つ導電性をも併せ持つ複合機能微粒子、それを用いた機能性膜を提供することを目的とする。
Accordingly, an object of the present invention is to provide composite fine particles in which metal ultrafine particles are bonded to the surface of many semiconductors or insulators, particularly highly transparent conductive fine particles, and a method for producing the same.
Another object of the present invention is to provide a simple and rapid method for producing the composite fine particles.
Another object of the present invention is to provide composite functional fine particles that retain the physical properties of the core compound and also have conductivity, and functional films using the same.
本発明は、
（１）平均粒子径が２〜１００ｎｍである半導体微粒子又は絶縁体微粒子の表面に、少なくとも１種のカップリング剤もしくはその加水分解物を介して、平均粒子径１〜２０ｎｍの金属超微粒子を結合させたことを特徴とする複合微粒子、
（２）前記カップリング剤が下記一般式〔Ｉ〕で表される化合物であることを特徴とする（１）項に記載の複合微粒子、
The present invention
(1) Ultrafine metal particles having an average particle diameter of 1 to 20 nm are bonded to the surface of semiconductor fine particles or insulator fine particles having an average particle diameter of 2 to 100 nm via at least one coupling agent or a hydrolyzate thereof. Composite fine particles characterized by
(2) The composite microparticle according to (1), wherein the coupling agent is a compound represented by the following general formula [I]:
（一般式〔Ｉ〕において、Ｍは２価ないし５価の原子価を有する金属を表わし、ｎは金属の原子価に相当する整数を表わす。Ｒは有機性基を表し、ｎ個のＲは同じでも異なっていてもよく、ｎ個のＲのうちの少なくとも２つは半導体微粒子、絶縁体微粒子又は金属超微粒子と反応性を有する基である。）、
（３）前記金属超微粒子が２０℃における比抵抗が２０μΩ・ｃｍ以下である金属からなることを特徴とする（１）又は（２）項に記載の複合微粒子、
（４）平均粒子径が２〜１００ｎｍである半導体微粒子又は絶縁体微粒子を含有する分散液に、少なくとも１種のカップリング剤を添加し該半導体微粒子又は該絶縁体微粒子と反応させた後、金属超微粒子を直接添加することにより、又は金属塩及び還元剤を添加し還元することにより、平均粒子径１〜２０ｎｍの金属超微粒子を該カップリング剤もしくはその加水分解物を介して、該半導体微粒子又は該絶縁体微粒子の表面に結合させることを特徴とする複合微粒子の製造方法、
（５）少なくとも１種のカップリング剤を含有する溶液中に、金属超微粒子を直接添加することにより、又は金属塩及び還元剤を添加し還元することにより、平均粒子径１〜２０ｎｍの金属超微粒子を該カップリング剤と結合させた後、平均粒子径２〜１００ｎｍである半導体微粒子又は絶縁体微粒子を含有する分散液を添加して該カップリング剤と反応させることにより、該金属超微粒子を、該カップリング剤もしくはその加水分解物を介して、該半導体微粒子又は該絶縁体微粒子の表面に結合することを特徴とする複合微粒子の製造方法、
（６）前記カップリング剤が下記一般式〔Ｉ〕で表される化合物であることを特徴とする上記（４）又は（５）項に記載の複合微粒子の製造方法、
(In the general formula [I], M represents a metal having a valence of 2 to 5, n represents an integer corresponding to the valence of the metal, R represents an organic group, and n R's represent They may be the same or different, and at least two of the n Rs are groups reactive with semiconductor fine particles, insulator fine particles or metal ultrafine particles).
(3) The composite ultrafine particles according to (1) or (2), wherein the ultrafine metal particles are made of a metal having a specific resistance at 20 ° C. of 20 μΩ · cm or less,
(4) After adding at least one coupling agent to a dispersion containing semiconductor fine particles or insulator fine particles having an average particle diameter of 2 to 100 nm and reacting with the semiconductor fine particles or the insulator fine particles, the metal By adding ultrafine particles directly, or by adding and reducing a metal salt and a reducing agent, ultrafine metal particles having an average particle diameter of 1 to 20 nm are converted into the semiconductor fine particles via the coupling agent or a hydrolyzate thereof. Or a method of producing composite fine particles, characterized by being bonded to the surface of the insulator fine particles,
(5) By adding metal ultrafine particles directly to a solution containing at least one coupling agent, or by adding and reducing a metal salt and a reducing agent, the metal ultrafine particles having an average particle diameter of 1 to 20 nm After the fine particles are combined with the coupling agent, a dispersion liquid containing semiconductor fine particles or insulator fine particles having an average particle diameter of 2 to 100 nm is added and reacted with the coupling agent, whereby the ultrafine metal particles are obtained. A method for producing composite fine particles characterized by binding to the surface of the semiconductor fine particles or the insulating fine particles via the coupling agent or a hydrolyzate thereof,
(6) The method for producing composite fine particles according to (4) or (5) above, wherein the coupling agent is a compound represented by the following general formula [I]:
（一般式〔Ｉ〕において、Ｍは２価ないし５価の原子価を有する金属を表わし、ｎは金属の原子価に相当する整数を表わす。Ｒは有機性基を表し、ｎ個のＲは同じでも異なっていてもよく、ｎ個のＲのうちの少なくとも２つは半導体微粒子、絶縁体微粒子又は金属超微粒子と反応性を有する基である。）、および、
（７）前記金属超微粒子が２０℃における比抵抗が２０μΩ・ｃｍ以下である金属からなることを特徴とする上記（４）〜（６）のいずれか１項に記載の複合微粒子の製造方法を提供するものである。
（８）上記（１）〜（３）のいずれか１項に記載の複合微粒子を含有する膜。
（９）上記（４）〜（７）のいずれか１項に記載の方法で製造された複合微粒子を含有する膜。
(In the general formula [I], M represents a metal having a valence of 2 to 5, n represents an integer corresponding to the valence of the metal, R represents an organic group, and n R's represent They may be the same or different, and at least two of the n R are groups reactive with semiconductor fine particles, insulator fine particles or metal ultrafine particles), and
(7) The method for producing composite fine particles according to any one of (4) to (6) above, wherein the ultrafine metal particles are made of a metal having a specific resistance of 20 μΩ · cm or less at 20 ° C. It is to provide.
(8) A film containing the composite fine particles according to any one of (1) to (3) above.
(9) A film containing composite fine particles produced by the method according to any one of (4) to (7) above.
少なくとも１種のカップリング剤もしくはその加水分解物を介して、半導体又は絶縁体微粒子の表面に金属超微粒子を結合させるため、無機物、有機物を問わず、各種半導体又は絶縁体を容易にコアの化合物の物性を保持した状態で導電性にすることができる。これにより、大面積の透明導電層を簡単、迅速に形成、提供することができる。 Since the metal ultrafine particles are bonded to the surface of the semiconductor or insulator fine particles via at least one coupling agent or a hydrolyzate thereof, various semiconductors or insulators can be easily incorporated into the core compound regardless of whether they are inorganic or organic. It is possible to make it conductive while maintaining its physical properties. Thereby, a transparent conductive layer having a large area can be formed and provided easily and quickly.
［カップリング剤］
本発明で用いるカップリング剤は、分子中に反応基を２つ以上有し、その中の少なくとも一つが半導体又は絶縁体微粒子と結合し、残りの少なくとも一つが金属超微粒子と結合することにより、半導体又は絶縁体微粒子と金属超微粒子との橋かけを行なうものである。カップリング剤はその加水分解物が半導体又は絶縁体微粒子と金属超微粒子との橋かけを行なうものであってもよい。
[Coupling agent]
The coupling agent used in the present invention has two or more reactive groups in the molecule, and at least one of them is bonded to the semiconductor or insulating fine particles, and at least one of the remaining is bonded to the metal ultrafine particles, Crosslinking between semiconductor or insulator fine particles and metal ultrafine particles is performed. The coupling agent may be one in which the hydrolyzate crosslinks the semiconductor or insulating fine particles and the metal ultrafine particles.
好ましい本発明のカップリング剤は、下記一般式〔Ｉ〕で表わされるものである。 A preferred coupling agent of the present invention is represented by the following general formula [I].
一般式〔Ｉ〕において、Ｍは２価ないし５価の原子価を有する金属を表わし、ｎは金属の原子価に相当する整数を表わす。Ｒは有機性基を表し、ｎ個のＲは同じでも異なっていてもよく、ｎ個のＲのうちの少なくとも２つは半導体微粒子、絶縁体微粒子又は金属超微粒子と反応性を有する基である。 In the general formula [I], M represents a metal having a divalent to pentavalent valence, and n represents an integer corresponding to the valence of the metal. R represents an organic group, and the n Rs may be the same or different, and at least two of the n Rs are groups having reactivity with semiconductor fine particles, insulator fine particles or metal ultrafine particles. .
Ｍは２価ないし５価の原子価を有する金属を表わすが、該金属としては、IIＢ族、IIIＡ族、IIIＢ族、IVＡ族、IVＢ族、VＡ族、VＢ族から選ばれる。好ましい金属としては、Ｚｎ、Ｓｉ、Ｇｅ、Ｓｎ、Ｐｂ、Ｔｉ、Ｖ、Ａｌ、Ｇａ、Ｉｎ、Ｓｂ、Ｂｉであり、特に好ましくはＳｉ、Ｔｉ、Ａｌである。 M represents a metal having a valence of 2 to 5. The metal is selected from Group IIB, Group IIIA, Group IIIB, Group IVA, Group IVB, Group VA and Group VB. Preferred metals are Zn, Si, Ge, Sn, Pb, Ti, V, Al, Ga, In, Sb, and Bi, and particularly preferred are Si, Ti, and Al.
Ｒで表わされる有機性基のうち、半導体微粒子、絶縁体微粒子又は金属超微粒子と反応性を有する基としては、例えば、（１）ビニル基、アリルオキシ基、アクリロキシ基、メタクリロキシ基、イソシアナト基、ホルミル基、エポキシ基、スチリル基、ウレイド基、ハロゲンなどの反応性基、又はこれらを末端に有するアルキル基、（２）末端に−ＳＨ、−ＣＮ、−ＮＨ２、−ＳＯ２ＯＨ、−ＳＯＯＨ、−ＯＰＯ（ＯＨ）２、−ＣＯＯＨなどの吸着性の基を有するアルキル基、（３）メトキシ基、エトキシ基、イソプロポキシ基、ｎ−プロポキシ基、ｔ−ブトキシ基、ｎ−ブトキシ基などアルコキシ基、及び（４）フェノキシ基が挙げられる。これらのアルキル基、アルコキシ基及びフェノキシ基としては、炭素数が８以下のものが望ましい。また、これらのアルキル基、アルコキシ基及びフェノキシ基はさらに置換基を有していてもよい。
Ｒで表わされる残りの有機性基としては任意のものでよいが、好ましくは末端に炭素数が８以下のものである。
Among the organic groups represented by R, examples of the group having reactivity with semiconductor fine particles, insulator fine particles or metal ultrafine particles include (1) vinyl group, allyloxy group, acryloxy group, methacryloxy group, isocyanato group, formyl. group, an epoxy group, a styryl group, a ureido group, a reactive group such as a halogen, or an alkyl group having them end, (2) -SH terminated, -CN, -NH 2, -SO 2 OH, -SOOH, An alkyl group having an adsorptive group such as —OPO (OH) 2 or —COOH; (3) an alkoxy group such as a methoxy group, an ethoxy group, an isopropoxy group, an n-propoxy group, a t-butoxy group, or an n-butoxy group. And (4) a phenoxy group. As these alkyl group, alkoxy group and phenoxy group, those having 8 or less carbon atoms are desirable. Further, these alkyl group, alkoxy group and phenoxy group may further have a substituent.
The remaining organic group represented by R may be any group, but preferably has 8 or less carbon atoms at the terminal.
本発明に用いられるカップリング剤の具体例を列挙するが、これらの化合物に限定されるものではない。
Ｎ−（２−アミノエチル）−３−アミノプロピルメチルジメトキシシラン、Ｎ−（２−アミノエチル）−３−アミノプロピルトリメトキシシラン、３−アミノフェノキシジメチルビニルシラン、アミノフェニルトリメトキシシラン、３−アミノプロピルトリエトキシシラン、ビス（トリメトキシシリルプロピル）アミン、（ｐ−クロロメチル）フェニルトリメトキシシラン、（３−グリシドキシプロピル）トリメトキシシラン、３−メルカプトプロピルトリメトキシシラン、（３−グリシドキシプロピル）−３−メルカプトプロピルジメトキシシラン、ビニルトリクロロシラン、テトラエトキシシラン、チタニウムイソプロポキシド、チタニウムジクロライドジエトキシド、３−メルカプトプロピルチタニウムトリメトキシド、３−メルカプトプロピルトリエトキシゲルマン、３−メタクリルオキシプロピルトリエトキシゲルマン、アミノフェニルアルミニウムジメトキシド、アルミニウムイソプロポキシド、３−アミノプロピルゲルマニウムトリエトキシド、アミノプロピルインジウムジメトキシエトキシド、３−グリシドキシプロピルトリエトキシスズ、３−メタクリルオキシプロピルトリｔ−ブトキシスズ、Ｎ−（２−アミノエチル）−３−アミノプロピルメチルジメトキシスズ、ビニル−トリス（２−エトキシメトキシ）鉛（IV）、３−メタクリルオキシプロピルテトラメトキシアンチモン（Ｖ）、３−メルカプトプロピルビスマス（III）ジｔ−ペントキシド、３−アミノプロピルバナジウムジブトキシドオキシドなどが挙げられる。
Although the specific example of the coupling agent used for this invention is enumerated, it is not limited to these compounds.
N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminophenoxydimethylvinylsilane, aminophenyltrimethoxysilane, 3-amino Propyltriethoxysilane, bis (trimethoxysilylpropyl) amine, (p-chloromethyl) phenyltrimethoxysilane, (3-glycidoxypropyl) trimethoxysilane, 3-mercaptopropyltrimethoxysilane, (3-glycid Xylpropyl) -3-mercaptopropyldimethoxysilane, vinyltrichlorosilane, tetraethoxysilane, titanium isopropoxide, titanium dichloride diethoxide, 3-mercaptopropyltitanium trimethoxide, 3-mercap Propyltriethoxygermane, 3-methacryloxypropyltriethoxygermane, aminophenylaluminum dimethoxide, aluminum isopropoxide, 3-aminopropylgermanium triethoxide, aminopropylindium dimethoxyethoxide, 3-glycidoxypropyltriethoxytin 3-methacryloxypropyltri-t-butoxytin, N- (2-aminoethyl) -3-aminopropylmethyldimethoxytin, vinyl-tris (2-ethoxymethoxy) lead (IV), 3-methacryloxypropyltetramethoxyantimony (V), 3-mercaptopropyl bismuth (III) di-t-pentoxide, 3-aminopropyl vanadium dibutoxide oxide, etc. are mentioned.
［半導体微粒子］
本発明における半導体微粒子は平均粒子径が２〜１００ｎｍ、好ましくは３〜５０ｎｍである。平均粒子径が小さすぎると半導体の結晶性が低下し、光吸収や発光特性、高屈折率性などの目的とする物性が得られなくなる可能性がある。一方大きすぎると分散物組成物や薄膜にした場合の透明性が低下する場合がある。
本発明の半導体微粒子の組成は特に制限はない。具体例としては、Ｃ、Ｓｉ、Ｇｅ、Ｓｎなどの周期表第１４族元素の単体、Ｓｅ、Ｔｅなどの周期表第１６族元素の単体、ＳｉＣなどの複数の周期表第１４族元素からなる化合物、ＡｌＳｂ、ＧａＰ、ＧａＡｓ、ＧａＳｂ、ＩｎＰ、ＩｎＡｓ，ＩｎＳｂ、ＧａＮ、ＩｎＧａＮ、ＩｎＡｌＮ、ＩｎＮ、ＢＮなどの周期表第１３族元素と周期表第１５族元素との化合物（III−Ｖ族化合物半導体）、ＺｎＯ、ＺｎＳ、ＺｎＳｅ、ＺｎＴｅ、ＣｄＳ、ＣｄＳｅ、ＣｄＴｅ、ＨｇＳｅ、ＨｇＴｅなどの周期表第１２族元素と周期表第１６族元素との化合物（II−VI族化合物半導体）、ＳｎＯ２、ＳｎＳ、ＳｎＳｅ、ＰｂＳ、ＰｂＳｅ、ＰｂＴｅなどの周期表第１４族元素と周期表第１６族元素との化合物（IV−VI族化合物半導体）、Ｓｂ２Ｓ３、Ｂｉ２Ｔｅ３、Ａｓ２Ｓｅ３などの周期表第１５族元素と周期表第１６族元素との化合物（V−VI族化合物半導体）、Ｃｕ２Ｏ、Ｃｕ２Ｓなどの周期表第１１族元素と周期表第１６族元素との化合物（I−VI族化合物半導体）、ＣｕＣｌ、ＣｕＢｒ、ＣｕＩ、ＡｇＣｌ、ＡｇＢｒなどの周期表第１１族元素と周期表第１７族元素との化合物、Ｆｅ２Ｏ３、Ｆｅ３Ｏ４、ＦｅＳなどの周期表第８族元素と周期表第１６族元素との化合物、ＴｉＯ２、Ｔｉ２Ｏ５、ＺｒＯ２などの周期表第４族元素と周期表第１６族元素との化合物、Ｙ２Ｏ３、Ｌａ２Ｏ３などの周期表第３族元素（ランタノイド元素を含む）と周期表第１６族元素との化合物などが挙げられる。
[Semiconductor fine particles]
The semiconductor fine particles in the present invention have an average particle diameter of 2 to 100 nm, preferably 3 to 50 nm. If the average particle size is too small, the crystallinity of the semiconductor is lowered, and there is a possibility that desired physical properties such as light absorption, light emission characteristics, and high refractive index properties cannot be obtained. On the other hand, if it is too large, the transparency in the case of a dispersion composition or a thin film may be lowered.
The composition of the semiconductor fine particles of the present invention is not particularly limited. Specific examples include a group 14 element of the periodic table such as C, Si, Ge, and Sn, a group 16 element of the periodic table such as Se and Te, and a plurality of group 14 elements of the periodic table such as SiC. Compound, compound of group 13 element of periodic table and group 15 element of periodic table (III-V group compound semiconductor, such as AlSb, GaP, GaAs, GaSb, InP, InAs, InSb, GaN, InGaN, InAlN, InN, BN) ), ZnO, ZnS, ZnSe, ZnTe, CdS, CdSe, CdTe, HgSe, HgTe, etc., a compound of a periodic table group 12 element and a periodic table group 16 element (II-VI group compound semiconductor), SnO 2 , SnS , SnSe, PbS, PbSe, compounds of the periodic table group 14 element and periodic table group 16 element such as PbTe (IV-VI group compound semiconductor), Sb 2 S 3, Bi Te 3, As 2 Se 3 of the periodic table Group 15 element and the periodic table compounds of Group 16 elements such as (V-VI group compound semiconductor), the periodic table Group 11 element such as Cu 2 O, Cu 2 S Compound (group I-VI compound semiconductor) with group 16 element of the periodic table, compound of group 11 element of periodic table and group 17 element of the periodic table such as CuCl, CuBr, CuI, AgCl, AgBr, Fe 2 O 3 , Fe 3 O 4 , FeS and other periodic table group 8 elements and periodic table group 16 elements, TiO 2 , Ti 2 O 5 and ZrO 2 periodic table group 4 elements and periodic table group 16 Examples thereof include compounds with elements, compounds of periodic table group 3 elements (including lanthanoid elements) such as Y 2 O 3 and La 2 O 3 and periodic table group 16 elements.
上記の例示した組成の半導体微粒子には、必要に応じて微量の他元素、例えばＭｎ、Ａｌ、Ｃｕ、Ａｇ、Ｚｎ、Ｃｌ、Ｃｅ、Ｅｕ、Ｔｂ、Ｅｒなどをドープしてもよい。また、ＺｎＳ（シェル）で被覆したＣｄＳｅ（コア）のようにいわゆるコア／シェル構造であってもよい。さらに透明導電材料として公知のＡＴＯ（ＳｂドープＳｎＯ２）、ＰＴＯ（ＰドープＳｎＯ２）、ＩＴＯ（ＳｎドープＩｎ２Ｏ３）、ＩＺＯ（ＺｎドープＩｎ２Ｏ３）、ＧＺＯ（ＧａドープＺｎＯ）、ＡＺＯ（ＡｌドープＺｎＯ）などの微粒子であってもよい。 The semiconductor fine particles having the above exemplified composition may be doped with a trace amount of other elements such as Mn, Al, Cu, Ag, Zn, Cl, Ce, Eu, Tb, Er and the like as necessary. Also, a so-called core / shell structure such as CdSe (core) coated with ZnS (shell) may be used. Furthermore, known ATO (Sb-doped SnO 2 ), PTO (P-doped SnO 2 ), ITO (Sn-doped In 2 O 3 ), IZO (Zn-doped In 2 O 3 ), GZO (Ga-doped ZnO) as transparent conductive materials, Fine particles such as AZO (Al-doped ZnO) may be used.
［絶縁体微粒子］
本発明における絶縁体微粒子は、前記半導体微粒子と同様に平均粒子径が２〜１００ｎｍ、好ましくは３〜５０ｎｍである。絶縁体としては、例えば、ポリメチルメタクリレート、ポリスチレン、ポリカーボネート、ポリエチレンテレフタレート、ポリオレフィンなどの多くの有機高分子、シリカ、アルミナなどの無機酸化物が挙げられる。
[Insulator fine particles]
The insulator fine particles in the present invention have an average particle diameter of 2 to 100 nm, preferably 3 to 50 nm, like the semiconductor fine particles. Examples of the insulator include many organic polymers such as polymethyl methacrylate, polystyrene, polycarbonate, polyethylene terephthalate, and polyolefin, and inorganic oxides such as silica and alumina.
［金属超微粒子］
本発明における金属超微粒子は、２０℃における比抵抗が２０μΩ・ｃｍ以下（好ましくは１０μΩ・ｃｍ以下、より好ましくは６μΩ・ｃｍ以下）である金属または複合金属からなるものであることが好ましい。一般的に、金属または複合金属の物性値は、バルクと粒子とでは異なることが知られているが、前記比抵抗の範囲は、金属または複合金属のバルクの値をいう。したがって、かかる物性値は「化学便覧（日本化学会編）」、「分析化学便覧（日本分析化学会編）」などの文献に記載されている。
[Ultrafine metal particles]
The ultrafine metal particles in the present invention are preferably made of a metal or a composite metal having a specific resistance at 20 ° C. of 20 μΩ · cm or less (preferably 10 μΩ · cm or less, more preferably 6 μΩ · cm or less). Generally, it is known that the physical property value of a metal or a composite metal is different between a bulk and a particle, but the specific resistance range refers to a bulk value of the metal or the composite metal. Therefore, such physical property values are described in documents such as “Chemical Handbook (Edited by the Chemical Society of Japan)”, “Analytical Chemical Handbook (Edited by the Chemical Society of Japan)”, and the like.
上記条件を満足する金属としては、Ａｕ、Ａｇ、Ｃｕ、Ｚｎ、Ｃｄ、Ａｌ、Iｎ、Ｔｌ、Ｓｎ、Ｃｏ、Ｎｉ、Ｆｅ、Ｐｄ、Ｉｒ、Ｍｏ、Ｐｔ、Ｒｕ、Ｗなどが挙げられる。これらの中でもＡｕ、Ａｇ、Ｃｕ、Ｐｔ、Ｐｄ、Ｎｉ、ＲｕおよびＳｎが比抵抗が小さくかつ酸化されにくいので好ましい。複合金属からなる場合には、Ａｕ、Ａｇ、Ｃｕ、Ｐｔ、Ｐｄ、Ｎｉ、ＲｕおよびＳｎの少なくとも１種含有する複合金属を用いるのが好ましい。かかる複合金属としては、Ｃｕ−Ｚｎ、Ｃｕ−Ｓｎ、Ａｌ−Ｃｕ、Ｃｕ−Ｓｎ−Ｐ、Ｃｕ−Ｎｉ、Ａｕ−Ａｇ−Ｃｕ、Ａｕ−Ｚｎ、Ａｕ−Ｎｉ、Ａｇ−Ｃｕ−Ｚｎ、Ａｇ−Ｃｕ−Ｚｎ−Ｓｎ、Ｓｎ−Ｐｂ、Ａｇ−Iｎ、Ｃｕ−Ａｇ−Ｎｉ、Ａｇ−Ｐｄなどが挙げられるが、これらに限定されるものではない。複合金属中の各金属の組成比については特に制限はなく、種々選択できる。また、金属および複合金属は不純物元素を含んでいてもよいが、その量は１％未満であるのが好ましい。不純物元素としては、Ｃｒ、Ｓｂ、Ｂｉ、Ｒｈなどの金属、また金属以外にも、Ｐ、Ｂ、Ｃ、Ｎ、Ｓなどの非金属、Ｎａ、Ｋなどのアルカリ金属、およびＭｇ、Ｃａなどのアルカリ土類金属が挙げられる。これらの不純物元素は、１種もしくは２種以上含有されていてもよい。 Examples of the metal that satisfies the above conditions include Au, Ag, Cu, Zn, Cd, Al, In, Tl, Sn, Co, Ni, Fe, Pd, Ir, Mo, Pt, Ru, and W. Among these, Au, Ag, Cu, Pt, Pd, Ni, Ru, and Sn are preferable because of their low specific resistance and resistance to oxidation. In the case of a composite metal, it is preferable to use a composite metal containing at least one of Au, Ag, Cu, Pt, Pd, Ni, Ru, and Sn. Such composite metals include Cu—Zn, Cu—Sn, Al—Cu, Cu—Sn—P, Cu—Ni, Au—Ag—Cu, Au—Zn, Au—Ni, Ag—Cu—Zn, and Ag—. Examples thereof include, but are not limited to, Cu—Zn—Sn, Sn—Pb, Ag—In, Cu—Ag—Ni, and Ag—Pd. There is no restriction | limiting in particular about the composition ratio of each metal in a composite metal, It can select variously. Further, the metal and the composite metal may contain an impurity element, but the amount is preferably less than 1%. Examples of the impurity element include metals such as Cr, Sb, Bi, and Rh, and non-metals such as P, B, C, N, and S, alkali metals such as Na and K, and Mg and Ca. Examples include alkaline earth metals. One or more of these impurity elements may be contained.
本発明に用いられる金属超微粒子の平均粒子径は１〜２０ｎｍ、好ましくは２〜１０ｎｍである。平均粒子径は、製造条件を適宜設定変更することで調整できる。 The average particle diameter of the ultrafine metal particles used in the present invention is 1 to 20 nm, preferably 2 to 10 nm. The average particle diameter can be adjusted by appropriately changing the production conditions.
［複合微粒子の製造方法］
表面修飾剤の説明
本発明においては、公知の表面修飾剤又は分散剤が複合微粒子合成時、あるいは合成後共存していてもよい。表面修飾剤又は分散剤としては、−ＳＨ、−ＣＮ、−ＮＨ2、−ＳＯ２ＯＨ、−ＳＯＯＨ、−ＯＰＯ（ＯＨ）2、−ＣＯＯＨ等の官能基を有する吸着性化合物や、アニオン、ノニオン、フッ素系界面活性剤が有効である。また、低分子化合物であっても高分子化合物であってもよい。具体的には、ポリエチレングリコール、ポリオキシエチレン（１）ラウリルエーテルリン酸、ラウリルエーテルリン酸、トリオクチルホスフィン、トリオクチルホスフィンオキシド、ポリリン酸ナトリウム、ビス（２−エチルヘキシル）スルホこはく酸ナトリウム、ドデシルベンゼンスルホン酸ナトリウム、ポリアクリル酸及びその塩、ポリメタクリル酸及びその塩、ポリビニルアルコール、ポリビニルピロリドン、ヒドロキシエチルセルロースなどが挙げられる。
[Production method of composite fine particles]
Description of Surface Modifier In the present invention, a known surface modifier or dispersant may be present at the time of composite fine particle synthesis or after synthesis. Examples of the surface modifier or dispersant include adsorptive compounds having functional groups such as —SH, —CN, —NH 2 , —SO 2 OH, —SOOH, —OPO (OH) 2 , —COOH, anions, and nonions. Fluorine surfactants are effective. Further, it may be a low molecular compound or a high molecular compound. Specifically, polyethylene glycol, polyoxyethylene (1) lauryl ether phosphate, lauryl ether phosphate, trioctyl phosphine, trioctyl phosphine oxide, sodium polyphosphate, bis (2-ethylhexyl) sulfosuccinate sodium, dodecylbenzene Examples thereof include sodium sulfonate, polyacrylic acid and a salt thereof, polymethacrylic acid and a salt thereof, polyvinyl alcohol, polyvinyl pyrrolidone, and hydroxyethyl cellulose.
還元剤の説明
本発明で用いる還元剤としては、無機還元剤でも有機還元剤でも良い。無機還元剤としては、ＮａＢＨ４、ヒドラジン、ヒドロキシルアミン又は水素ガス等が挙げられる。また有機還元剤としては、（１）ヒドラジン基を含有するヒドラジン系化合物類（例えばフェニルヒドラジン等）、（２）ｐ−フェニレンジアミン、エチレンジアミン、ｐ−アミノフェノール等のアミン類、（３）窒素原子にアシル基やアルコキシカルボニル基などが置換したヒドロキシルアミン系化合物類、（４）２−ジメチルアミノエタノール、２−ジエチルアミノエタノール、２−アミノエタノール、ジエタノールアミン、２−アミノ−２−メチル−１−プロパノール等のアミノアルコール類、（５）ヒドロキノン、カテコール、１,４−ブタンジオール、エチレングリコール等のジオール類、又は（６）一般式：
Ｘ−（Ａ＝Ｂ）ｎ−Ｙ（ただし、Ａ及びＢはそれぞれ炭素原子又は窒素原子を表し、Ｘ及びＹはそれぞれ非共有電子対を有する原子がＡ及びＢに結合する原子団を表し、ｎは０〜３を表す。）により表される有機還元剤又はその互変異性体、又は熱的にこれらを生成する化合物類（例えば、ヒドロキシアセトン等の特願２００４−１８８９５号明細書に記載の化合物）等が挙げられる。これらの還元剤は、単独または併用で用いることができる。
Description of Reducing Agent The reducing agent used in the present invention may be an inorganic reducing agent or an organic reducing agent. Examples of the inorganic reducing agent include NaBH 4 , hydrazine, hydroxylamine or hydrogen gas. Examples of the organic reducing agent include (1) hydrazine-based compounds containing a hydrazine group (for example, phenylhydrazine), (2) amines such as p-phenylenediamine, ethylenediamine, and p-aminophenol, and (3) nitrogen atom. Hydroxylamine compounds substituted with acyl group or alkoxycarbonyl group, (4) 2-dimethylaminoethanol, 2-diethylaminoethanol, 2-aminoethanol, diethanolamine, 2-amino-2-methyl-1-propanol, etc. (5) hydroquinone, catechol, 1,4-butanediol, diols such as ethylene glycol, or (6) general formula:
X- (A = B) n -Y (where A and B each represent a carbon atom or a nitrogen atom, X and Y each represent an atomic group in which an atom having an unshared electron pair is bonded to A and B, n represents an organic reducing agent represented by 0 to 3, or a tautomer thereof, or a compound that thermally generates them (for example, described in Japanese Patent Application No. 2004-18895 such as hydroxyacetone). Compound) and the like. These reducing agents can be used alone or in combination.
本発明の好ましい態様では、平均粒子径が２〜１００ｎｍである上記半導体微粒子又は上記絶縁体微粒子を含有する分散液に、少なくとも１種の上記カップリング剤を添加し半導体又は絶縁体微粒子と反応させた後、金属超微粒子を直接添加することにより、又は金属塩及び還元剤を添加し還元することにより、平均粒子径１〜２０ｎｍの金属超微粒子を、カップリング剤もしくはその加水分解物を介して、半導体又は絶縁体微粒子の表面に結合させて複合微粒子を製造する。また、別の好ましい態様では、少なくとも１種の上記カップリング剤を含有する溶液中に、金属超微粒子を直接添加することにより、又は金属塩及び還元剤を添加し還元することにより、平均粒子径１〜２０ｎｍの金属超微粒子をカップリング剤と結合させた後、平均粒子径２〜１００ｎｍである上記半導体微粒子又は上記絶縁体微粒子を含有する分散液を添加してカップリング剤と反応させることにより、金属超微粒子を、カップリング剤もしくはその加水分解物を介して、半導体又は絶縁体微粒子の表面に結合させて複合微粒子を製造する。なお、半導体又は絶縁体微粒子の表面にカップリング剤を結合させる反応と、金属超微粒子を添加又は生成させてその表面にカップリング剤を結合させる反応とを同時に行なうこともできる。
本発明において、好ましく用いることができる金属塩としては、上記金属のハロゲン化物、酢酸塩などのカルボン酸塩、硝酸塩、硫酸塩、アセチルアセトナート化合物等が挙げられる。
また、上記分散液に好ましく用いられる溶媒としては、特に制限はなく、水、アルコール類（メタノール、エタノール、２−プロパノール等）、カルボン酸エステル類（酢酸エチル、酢酸ブチル等）、ケトン類（メチルエチルケトン、シクロヘキサノン等）、アミド（Ｎ、Ｎ−ジメチルホルムアミド、Ｎ−メチルホルムアミド等）類が挙げられる。
In a preferred embodiment of the present invention, at least one coupling agent is added to the dispersion containing the semiconductor fine particles or the insulating fine particles having an average particle diameter of 2 to 100 nm to react with the semiconductor or insulating fine particles. Then, by adding metal ultrafine particles directly, or by adding and reducing metal salts and reducing agents, ultrafine metal particles with an average particle diameter of 1 to 20 nm are converted via a coupling agent or a hydrolyzate thereof. The composite fine particles are produced by bonding to the surface of the semiconductor or insulator fine particles. In another preferred embodiment, the average particle size is obtained by directly adding ultrafine metal particles or by adding a metal salt and a reducing agent to a solution containing at least one coupling agent. After binding ultrafine metal particles of 1 to 20 nm with a coupling agent, a dispersion containing the semiconductor fine particles or the insulating fine particles having an average particle diameter of 2 to 100 nm is added and reacted with the coupling agent. The ultrafine metal particles are bonded to the surface of the semiconductor or insulating fine particles via a coupling agent or a hydrolyzate thereof to produce composite fine particles. In addition, the reaction for binding the coupling agent to the surface of the semiconductor or insulator fine particles and the reaction for adding or generating metal ultrafine particles to bond the coupling agent to the surface can be performed simultaneously.
Examples of metal salts that can be preferably used in the present invention include halides of the above metals, carboxylates such as acetates, nitrates, sulfates, acetylacetonate compounds, and the like.
Moreover, there is no restriction | limiting in particular as a solvent preferably used for the said dispersion liquid, Water, alcohols (methanol, ethanol, 2-propanol, etc.), carboxylic acid esters (ethyl acetate, butyl acetate, etc.), ketones (methyl ethyl ketone) And cyclohexanone) and amides (N, N-dimethylformamide, N-methylformamide, etc.).
本発明の複合微粒子は、半導体又は絶縁体微粒子の質量当たり、金属超微粒子が少なくとも１／１０倍質量結合していることが好ましく、１／５倍質量結合していることがさらに好ましい。 In the composite fine particles of the present invention, it is preferable that the ultrafine metal particles are bonded at least 1/10 times, more preferably 1/5 times the mass bonding per mass of the semiconductor or insulator particles.
本発明の複合微粒子は、例えば、その分散物をスピンコート、バーコートなど常法により塗布して薄膜を簡単、迅速かつ大面積で形成することができる。得られる薄膜は、表面抵抗が小さく、透明性が高いので、透明導電層として好適である。この薄膜は、焼成によりさらに導電性が高まる。 The composite fine particles of the present invention can be formed, for example, by applying the dispersion by a conventional method such as spin coating or bar coating to form a thin film easily, rapidly and in a large area. The resulting thin film is suitable as a transparent conductive layer because it has low surface resistance and high transparency. This thin film further increases conductivity by firing.
本発明の金属超微粒子（金属ナノ粒子）の粒径評価には透過型電子顕微鏡（ＴＥＭ）やＸ線回折（ＸＲＤ）を用いた常法により行うことができる。 The particle size of the ultrafine metal particles (metal nanoparticles) of the present invention can be evaluated by a conventional method using a transmission electron microscope (TEM) or X-ray diffraction (XRD).
以下、本発明を実施例に基づきさらに詳細に説明するが、本発明はこれに限定されるものではない。 EXAMPLES Hereinafter, although this invention is demonstrated further in detail based on an Example, this invention is not limited to this.
実施例１ ［ＳｉＯ２微粒子へＡｕ超微粒子を結合した複合微粒子の合成］
触媒化成工業（株）製中空シリカ微粒子のＩＰＡ（イソプロピルアルコール）分散物（ＣＳ−６０；平均粒子径５０ｎｍ）３．６ｍｌ、３−メルカプトプロピルトリメトキシシラン０．７ｍｌ、およびアルミニウムイソプロポキシド４ｍｇをＭＥＫ（エチルメチルケトン）１５０ｍｌに添加し混合した。さらに水０．２２ｍｌを加えて６０℃に昇温し４時間撹拌し反応させた。その後、塩化金（III）酸四水和物０．８４ｇをＭＥＫ２０ｍｌに溶解して添加し、さらにヒドロキシアセトン１．５ｍｌを添加して３０分撹拌した。液温を室温まで下げて得られた分散物をＴＥＭおよびＸＲＤで解析したところ、中空シリカ微粒子上一面に粒子径３〜５ｎｍのＡｕの超微粒子が結合しているのが観察された。図１にＴＥＭの写真を示す。なお、図２は塩化金（III）酸を添加しない場合のＴＥＭ写真である。
Example 1 [Synthesis of composite fine particles in which Au ultrafine particles are bonded to SiO 2 fine particles]
3.6 ml of IPA (isopropyl alcohol) dispersion (CS-60; average particle size 50 nm) of hollow silica fine particles manufactured by Catalyst Kasei Kogyo Co., Ltd., 0.7 ml of 3-mercaptopropyltrimethoxysilane, and 4 mg of aluminum isopropoxide The mixture was added to 150 ml of MEK (ethyl methyl ketone) and mixed. Further, 0.22 ml of water was added, the temperature was raised to 60 ° C., and the mixture was stirred for 4 hours to be reacted. Thereafter, 0.84 g of gold chloride (III) acid tetrahydrate was dissolved in 20 ml of MEK and added, and 1.5 ml of hydroxyacetone was further added and stirred for 30 minutes. When the dispersion obtained by lowering the liquid temperature to room temperature was analyzed by TEM and XRD, it was observed that Au ultrafine particles having a particle diameter of 3 to 5 nm were bonded to the entire surface of the hollow silica fine particles. FIG. 1 shows a TEM photograph. FIG. 2 is a TEM photograph in the case where chloroauric (III) acid is not added.
実施例２ ［塗布膜の評価］
この分散液９０ｍｌにＩＴＯインクＸ−１０１Ｈ（東北化工製）１０ｇを添加しビーズミルで分散してガラス基板上に乾燥膜厚が約１５０ｎｍになるようにスピンコートして８０℃で乾燥した。得られた薄膜の表面抵抗は５．２×１０５Ω／□、５５０ｎｍの波長における透過率は９０％であった。比較として、塩化金（III）酸を添加しない以外は実施例１と同様に調製した分散液９０ｍｌにＩＴＯインク１０ｇを添加してガラス基板上に乾燥膜厚約１５０ｎｍで塗布した薄膜の表面抵抗は６．９×１０６Ω／□、５５０ｎｍの波長における透過率は９４％であった。また、ＩＴＯインク１０ｇをＭＥＫ９０ｍｌで希釈してガラス基板上に乾燥膜厚約１５０ｎｍで塗布した薄膜の表面抵抗は２．１×１０６Ω／□、５５０ｎｍの波長における透過率は９２％であった。本発明の複合微粒子を添加することにより塗布膜の透過率はほとんど損なうことなく伝導度が大幅に改善されることがわかった。
Example 2 [Evaluation of Coating Film]
10 g of ITO ink X-101H (manufactured by Tohoku Kako) was added to 90 ml of this dispersion, dispersed with a bead mill, spin-coated on a glass substrate to a dry film thickness of about 150 nm, and dried at 80 ° C. The surface resistance of the obtained thin film was 5.2 × 10 5 Ω / □, and the transmittance at a wavelength of 550 nm was 90%. For comparison, the surface resistance of a thin film prepared by adding 10 g of ITO ink to 90 ml of a dispersion prepared in the same manner as in Example 1 except that no gold chloride (III) acid was applied and coating the glass substrate with a dry film thickness of about 150 nm is The transmittance at a wavelength of 6.9 × 10 6 Ω / □, 550 nm was 94%. Further, the surface resistance of a thin film obtained by diluting 10 g of ITO ink with 90 ml of MEK and coating it on a glass substrate with a dry film thickness of about 150 nm was 2.1 × 10 6 Ω / □, and the transmittance at a wavelength of 550 nm was 92%. . It has been found that by adding the composite fine particles of the present invention, the conductivity is greatly improved without substantially impairing the transmittance of the coating film.
実施例３ ［ＳｉＯ２微粒子へＡｇ超微粒子を結合した複合微粒子の合成］
実施例１において、塩化金（III）酸四水和物に代えて酢酸銀０．６９ｇを、またヒドロキシアセトンに代えてヒドラジン一水和物１ｍｌを用いた以外は同様にして、中空シリカ微粒子にＡｇ超微粒子が結合した複合微粒子を合成した。実施例１と同様にして得られたこの複合微粒子の薄膜（膜厚約１５０ｎｍ）の表面抵抗は４．６×１０５Ω／□、５５０ｎｍの波長における透過率は９４％であった。
Example 3 [Synthesis of Composite Fine Particles Combining Ag 2 Fine Particles with SiO 2 Fine Particles]
In Example 1, the hollow silica fine particles were obtained in the same manner except that 0.69 g of silver acetate was used instead of gold chloride (III) acid tetrahydrate and 1 ml of hydrazine monohydrate was used instead of hydroxyacetone. Composite fine particles to which Ag ultrafine particles were bonded were synthesized. The composite fine particles obtained in the same manner as in Example 1 had a surface resistance of 4.6 × 10 5 Ω / □ and a transmittance of 94% at a wavelength of 550 nm.
実施例４ ［ＴｉＯ２微粒子へＡｕ超微粒子を結合した複合微粒子の合成］
塩化白金（IV）酸六水和物１．０６ｇをＭＥＫ１００ｍｌに溶解し、３−メルカプトプロピルトリメトキシシラン０．７ｍｌを混合した。この溶液を強く撹拌しながらヒドラジン一水和物１ｍｌを添加し、Ｐｔ超微粒子を形成した。この中に、石原産業（株）製ＴｉＯ２微粒子（ＭＰＴ−１２９Ｂ；平均粒子径４０ｎｍ）１ｇにシクロヘキサノール２０ｍｌを添加してアイガーミルで１時間分散した液およびアルミニウムイソプロポキシド４ｍｇをシクロヘキサノン２０ｍｌに溶解した液を添加して撹拌した。さらに水０．２２ｍｌを加えて６０℃に昇温し４時間撹拌し反応させた。得られた分散物をＴＥＭおよびＸＲＤで解析したところ、ＴｉＯ２微粒子上一面に粒子径３〜５ｎｍのＰｔ超微粒子が結合しているのが観察された。この分散物を実施例２と同様にガラス基板上に乾燥膜厚が約１５０ｎｍになるように塗布して得られた薄膜の表面抵抗は６．５×１０５Ω／□、５５０ｎｍの波長における透過率は９０％であった。
Example 4 [Synthesis of composite fine particles in which Au ultrafine particles are bonded to TiO 2 fine particles]
1.06 g of chloroplatinic (IV) acid hexahydrate was dissolved in 100 ml of MEK, and 0.7 ml of 3-mercaptopropyltrimethoxysilane was mixed. While strongly stirring this solution, 1 ml of hydrazine monohydrate was added to form Pt ultrafine particles. In this, 20 ml of cyclohexanol was added to 1 g of TiO 2 fine particles (MPT-129B; average particle size 40 nm) manufactured by Ishihara Sangyo Co., Ltd. and dispersed for 1 hour in an Eiger mill and 4 mg of aluminum isopropoxide were dissolved in 20 ml of cyclohexanone The solution was added and stirred. Further, 0.22 ml of water was added, the temperature was raised to 60 ° C., and the mixture was stirred for 4 hours to be reacted. When the obtained dispersion was analyzed by TEM and XRD, it was observed that Pt ultrafine particles having a particle diameter of 3 to 5 nm were bonded to the entire surface of the TiO 2 fine particles. The surface resistance of a thin film obtained by applying this dispersion on a glass substrate in the same manner as in Example 2 so as to have a dry film thickness of about 150 nm is 6.5 × 10 5 Ω / □ and transmission at a wavelength of 550 nm. The rate was 90%.
実施例５
カップリング剤を３−メルカプトプロピルチタニウムトリメトキシドに代えた以外は実施例１と同様にＴｉＯ２微粒子へＰｔ超微粒子を結合した複合微粒子を合成した。
Example 5
Composite fine particles in which Pt ultrafine particles were bonded to TiO 2 fine particles were synthesized in the same manner as in Example 1 except that the coupling agent was changed to 3-mercaptopropyltitanium trimethoxide.
実施例６ ［焼成による表面抵抗の変化］
実施例２、３および４において作成したガラス基板に塗布した本発明のサンプルを２５０℃で３０分焼成した後、再度表面抵抗を測定したところ、いずれも１０４Ω／□のオーダー（比較サンプルは１０５Ω／□のオーダー）に低下していた。本発明の複合微粒子を塗布することにより形成した薄膜は焼成によりさらに導電性が高まることがわかった。
Example 6 [Change in surface resistance by firing]
The samples of the present invention applied to the glass substrates prepared in Examples 2, 3 and 4 were baked at 250 ° C. for 30 minutes, and then the surface resistance was measured again. As a result, both were on the order of 10 4 Ω / □ (comparative samples were 10 5 Ω / □). It was found that the conductivity of the thin film formed by applying the composite fine particles of the present invention is further increased by firing.
実施例７
塩化金（III）酸四水和物０．８４ｇをＭＥＫ８０ｍｌに溶解し、３−メルカプトプロピルトリメトキシシラン０．７ｍｌを混合した。この液にシクロヘキサノン２０ｍｌ及びソルスパースＧＲ２４０００（ＩＣＩ製）を６００ｍｇ添加した。この中に前記中空シリカ微粒子のＩＰＡ分散物ＣＳ−６０を３．６ｍｌ添加し、強く撹拌しながらヒドラジン一水和物１ｍｌを添加しＡｕ超微粒子を形成した。ガラス基板上に乾燥膜厚約１５０ｎｍで塗布し、１２０℃で乾燥した。同様のプロセスでサンプルを作製してＴＥＭ観察を行なったところ、中空シリカの表面にＡｕの微粒子が付着していた。ガラス基板上で直接複合微粒子の薄膜が形成できることがわかった。
Example 7
0.84 g of gold (III) chloride tetrahydrate was dissolved in 80 ml of MEK, and 0.7 ml of 3-mercaptopropyltrimethoxysilane was mixed. To this solution, 20 ml of cyclohexanone and 600 mg of Solsperse GR 24000 (manufactured by ICI) were added. Into this, 3.6 ml of the IPA dispersion CS-60 of hollow silica fine particles was added, and 1 ml of hydrazine monohydrate was added with vigorous stirring to form Au ultrafine particles. It apply | coated with the dry film thickness of about 150 nm on the glass substrate, and it dried at 120 degreeC. When a sample was prepared by the same process and observed by TEM, Au fine particles were adhered to the surface of the hollow silica. It was found that a thin film of composite fine particles can be formed directly on a glass substrate.
Claims (9)
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007179785A (en) * | 2005-12-27 | 2007-07-12 | Sanyo Chem Ind Ltd | Method of manufacturing conductive fine particles |
| JP2007179781A (en) * | 2005-12-27 | 2007-07-12 | Sanyo Chem Ind Ltd | Method of manufacturing conductive fine particles |
| JP2008147625A (en) * | 2006-10-13 | 2008-06-26 | Toyota Motor Engineering & Manufacturing North America Inc | Homogeneous thermoelectric nanocomposite material using core-shell nanoparticles |
| JP2009170320A (en) * | 2008-01-17 | 2009-07-30 | Toda Kogyo Corp | Conductive particle powder |
| JP2010033911A (en) * | 2008-07-29 | 2010-02-12 | Hiroshima Industrial Promotion Organization | Conductive particle and conductive material |
| JP2013065576A (en) * | 2012-12-27 | 2013-04-11 | Toda Kogyo Corp | Conductive particle powder |
| JP2014096371A (en) * | 2013-12-05 | 2014-05-22 | Hiroshima Industrial Promotion Organization | Conductive particle |
| JP2017128809A (en) * | 2017-02-15 | 2017-07-27 | 東洋製罐グループホールディングス株式会社 | Silver ultrafine particle-containing dispersion liquid and method for producing the same |
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2004
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007179785A (en) * | 2005-12-27 | 2007-07-12 | Sanyo Chem Ind Ltd | Method of manufacturing conductive fine particles |
| JP2007179781A (en) * | 2005-12-27 | 2007-07-12 | Sanyo Chem Ind Ltd | Method of manufacturing conductive fine particles |
| JP2008147625A (en) * | 2006-10-13 | 2008-06-26 | Toyota Motor Engineering & Manufacturing North America Inc | Homogeneous thermoelectric nanocomposite material using core-shell nanoparticles |
| JP2009170320A (en) * | 2008-01-17 | 2009-07-30 | Toda Kogyo Corp | Conductive particle powder |
| JP2010033911A (en) * | 2008-07-29 | 2010-02-12 | Hiroshima Industrial Promotion Organization | Conductive particle and conductive material |
| JP2013065576A (en) * | 2012-12-27 | 2013-04-11 | Toda Kogyo Corp | Conductive particle powder |
| JP2014096371A (en) * | 2013-12-05 | 2014-05-22 | Hiroshima Industrial Promotion Organization | Conductive particle |
| JP2017128809A (en) * | 2017-02-15 | 2017-07-27 | 東洋製罐グループホールディングス株式会社 | Silver ultrafine particle-containing dispersion liquid and method for producing the same |
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