JP2009144188A - Flat metal particle, production method therefor, composition containing flat metal particle, and infrared absorbing material - Google Patents
Flat metal particle, production method therefor, composition containing flat metal particle, and infrared absorbing material Download PDFInfo
- Publication number
- JP2009144188A JP2009144188A JP2007320985A JP2007320985A JP2009144188A JP 2009144188 A JP2009144188 A JP 2009144188A JP 2007320985 A JP2007320985 A JP 2007320985A JP 2007320985 A JP2007320985 A JP 2007320985A JP 2009144188 A JP2009144188 A JP 2009144188A
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- Prior art keywords
- flat metal
- particles
- particle
- compound
- silver
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229920000636 poly(norbornene) polymer Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920001230 polyarylate Polymers 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- ABKQFSYGIHQQLS-UHFFFAOYSA-J sodium tetrachloropalladate Chemical compound [Na+].[Na+].Cl[Pd+2](Cl)(Cl)Cl ABKQFSYGIHQQLS-UHFFFAOYSA-J 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
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Abstract
Description
本発明は、平板状金属粒子及び平板状金属粒子の製造方法、並びに平板状金属粒子含有組成物、及び赤外線吸収材料に関する。 The present invention relates to a flat metal particle, a method for producing a flat metal particle, a flat metal particle-containing composition, and an infrared absorbing material.
銀、金等の貴金属粒子は、化学的に安定であり、また、表面プラズモン共鳴により可視域に吸収を有するため、塗料等の着色剤としての応用が期待されている。例えば２００１年にＣ．Ａ．Ｍｉｒｋｉｎらにより、三角形状平板Ａｇ粒子の合成に関する報告がなされている（特許文献１及び非特許文献１参照）。この報告では、三角形状平板状Ａｇ粒子のサイズ、及び（サイズ／厚み）比により極大吸収波長が変化し、可視域〜近赤外域に吸収波長を制御できることが開示されている。このように可視域〜近赤外域に吸収域が広がったことにより、着色剤としてだけでなく、赤外線吸収剤としての応用も期待されている。 Since noble metal particles such as silver and gold are chemically stable and have absorption in the visible region due to surface plasmon resonance, application as a colorant for paints and the like is expected. For example, in 2001, C.I. A. A report on the synthesis of triangular tabular Ag particles has been made by Mirkin et al. (See Patent Document 1 and Non-Patent Document 1). This report discloses that the maximum absorption wavelength varies depending on the size of the triangular tabular Ag particles and the (size / thickness) ratio, and the absorption wavelength can be controlled from the visible region to the near infrared region. As described above, since the absorption range is expanded from the visible range to the near-infrared range, it is expected to be applied not only as a colorant but also as an infrared absorber.
そこで、平板状金属粒子の合成方法が種々検討されており、例えばＣ．Ａ．Ｍｉｒｋｉｎらによる光誘起法がある。この光誘起法は、銀ナノコロイド水溶液に７００ｎｍ未満の波長を有する光を照射することにより、銀ナノプリズムを形成する方法である（特許文献１、非特許文献１、及び非特許文献２参照）。
しかし、前記光誘起法により合成された銀ナノプリズムは、単一性は高いが、硝酸銀濃度が０．１ｍＭと低く、反応時間が２０〜５０時間と長いので、大量生産には不向きなものである。
Various methods for synthesizing tabular metal particles have been studied. A. There is a light-induced method by Mirkin et al. This photo-induced method is a method of forming silver nanoprisms by irradiating silver nanocolloid aqueous solution with light having a wavelength of less than 700 nm (see Patent Document 1, Non-Patent Document 1, and Non-Patent Document 2). .
However, although the silver nanoprism synthesized by the photo-induced method has high unity, the silver nitrate concentration is as low as 0.1 mM and the reaction time is as long as 20 to 50 hours, so it is not suitable for mass production. is there.
また、還元剤による平板状金属粒子の形成が検討されており、クエン酸を保護剤、ジメチルアミンボランを還元剤とし、水溶液中で硝酸銀から銀ナノプリズムを合成する方法が提案されている（特許文献２、３、及び４参照）。しかし、これらの提案の方法も、硝酸銀濃度が低く、反応時間が長くかかり、大量生産には不向きなものである。
また、ポリビニルピロリドン（ＰＶＰ）を保護剤として、硝酸銀をジメチルホルムアミド中で加熱還元する銀ナノプリズムの合成方法が報告されている（非特許文献３参照）。しかし、この合成方法は、ジメチルホルムアミドの沸点付近（１５６℃）までの加熱が必要であるため危険であり、また制御が難しいため単一性が低く、更にジメチルホルムアミドは環境負荷が大きいという問題がある。
In addition, the formation of flat metal particles with a reducing agent has been studied, and a method for synthesizing silver nanoprisms from silver nitrate in an aqueous solution using citric acid as a protective agent and dimethylamine borane as a reducing agent has been proposed (patent) References 2, 3, and 4). However, these proposed methods are also unsuitable for mass production because the silver nitrate concentration is low and the reaction time is long.
In addition, a method for synthesizing silver nanoprisms in which silver nitrate is heated and reduced in dimethylformamide using polyvinylpyrrolidone (PVP) as a protective agent has been reported (see Non-Patent Document 3). However, this synthesis method is dangerous because it requires heating to the vicinity of the boiling point of dimethylformamide (156 ° C.), is difficult to control, has low unity, and dimethylformamide has a large environmental burden. is there.
したがって大量生産が可能であり、短時間で高濃度の平板状金属粒子を効率よく合成でき、安全かつ環境影響の少ない平板状金属粒子の製造方法及び平板状金属粒子の速やかな提供が望まれているのが現状である。 Therefore, mass production is possible, high-density tabular metal particles can be efficiently synthesized in a short time, and a method for producing tabular metal particles that is safe and has little environmental impact and prompt provision of tabular metal particles are desired. The current situation is.
本発明は、従来における前記諸問題を解決し、以下の目的を達成することを課題とする。即ち、本発明は、大量生産が可能であり、短時間で高濃度の平板状金属粒子を効率よく合成でき、安全かつ環境影響の少ない平板状金属粒子の製造方法及び該製造方法により製造された平板状金属粒子、並びに平板状金属粒子含有組成物、及び赤外線吸収材料を提供することを目的とする。 An object of the present invention is to solve the above-described problems and achieve the following objects. That is, the present invention can be mass-produced, can efficiently synthesize high-concentration tabular metal particles in a short time, and is produced by a method for producing tabular metal particles that is safe and has little environmental impact, and the production method. It aims at providing a flat metal particle, a flat metal particle containing composition, and an infrared rays absorbing material.
前記課題を解決するための手段としては以下の通りである。即ち、
＜１＞ ポリオール化合物を含む溶媒中に金属化合物及びピロリドン化合物を添加した反応液を、４０℃以上該溶媒の沸点以下の温度で加熱することにより、平板状金属粒子を製造することを特徴とする平板状金属粒子の製造方法である。
＜２＞ 溶媒中にポリオール化合物を３０体積％以上含む前記＜１＞に記載の平板状金属粒子の製造方法である。
＜３＞ ポリオール化合物が、エチレングリコール、ジエチレングリコール、トリエチレングリコール、プロピレングリコール、グリセリン、及びポリエチレングリコールから選択される少なくとも１種を含有する前記＜１＞から＜２＞のいずれかに記載の平板状金属粒子の製造方法である。
＜４＞ 金属化合物における金属が、銀、金、白金、パラジウム、銅、ニッケル、及びコバルトから選択される少なくとも１種を含有する前記＜１＞から＜３＞のいずれかに記載の平板状金属粒子の製造方法である。
＜５＞ ピロリドン化合物がポリビニルピロリドンであり、該ポリビニルピロリドンが、ピロリドンユニットの繰り返し単位が８５以上である前記＜１＞から＜４＞のいずれかに記載の平板状金属粒子の製造方法である。
＜６＞ ピロリドン化合物と、金属化合物とのモル比（ピロリドン化合物／金属化合物）が４以上である前記＜１＞から＜５＞のいずれかに記載の平板状金属粒子の製造方法である。
＜７＞ 前記＜１＞から＜６＞のいずれかに記載の平板状金属粒子の製造方法により製造されたことを特徴とする平板状金属粒子である。
＜８＞ 粒子径が１０ｎｍ〜１，０００ｎｍであり、かつ平均アスペクト比（粒子径／粒子厚み）が１．１以上である前記＜７＞に記載の平板状金属粒子である。
＜９＞ 前記＜７＞から＜８＞のいずれかに記載の平均アスペクト比が１．１〜２０．０の平板状金属粒子を個数平均で３０％以上含有することを特徴とする平板状金属粒子含有組成物である。
＜１０＞ 前記＜９＞に記載の平板状金属粒子含有組成物からなる赤外線吸収層を少なくとも有することを特徴とする赤外線吸収材料である。
Means for solving the above problems are as follows. That is,
<1> A plate-like metal particle is produced by heating a reaction solution obtained by adding a metal compound and a pyrrolidone compound to a solvent containing a polyol compound at a temperature not lower than 40 ° C. and not higher than the boiling point of the solvent. It is a manufacturing method of a flat metal particle.
<2> The method for producing flat metal particles according to <1>, wherein the solvent contains a polyol compound in an amount of 30% by volume or more.
<3> The flat plate shape according to any one of <1> to <2>, wherein the polyol compound contains at least one selected from ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, glycerin, and polyethylene glycol. It is a manufacturing method of a metal particle.
<4> The flat metal according to any one of <1> to <3>, wherein the metal in the metal compound contains at least one selected from silver, gold, platinum, palladium, copper, nickel, and cobalt. A method for producing particles.
<5> The method for producing flat metal particles according to any one of <1> to <4>, wherein the pyrrolidone compound is polyvinylpyrrolidone, and the polyvinylpyrrolidone has 85 or more repeating units of pyrrolidone units.
<6> The method for producing flat metal particles according to any one of <1> to <5>, wherein a molar ratio of the pyrrolidone compound to the metal compound (pyrrolidone compound / metal compound) is 4 or more.
<7> Flat metal particles produced by the method for producing flat metal particles according to any one of <1> to <6>.
<8> The flat metal particles according to <7>, wherein the particle diameter is 10 nm to 1,000 nm, and the average aspect ratio (particle diameter / particle thickness) is 1.1 or more.
<9> A plate-like metal comprising a plate-like metal particle having an average aspect ratio of 1.1 to 20.0 according to any one of <7> to <8> in an average number of 30% or more. It is a particle-containing composition.
<10> An infrared absorbing material comprising at least an infrared absorbing layer made of the flat metal particle-containing composition according to <9>.
本発明の平板状金属粒子の製造方法においては、エチレングリコール等のポリオール化合物中で、ポリビニルピロリドン（ＰＶＰ）と共に、硝酸銀、塩化金酸等の金属化合物を加熱還元することにより、三角形、六角形状等の平板状金属粒子を得ることができる。得られた平板状金属粒子は、可視域から近赤外域に表面プラズモン共鳴由来の吸収を有しており、鮮やかな発色を示すため、インクジェット、カラーフィルタ等の色材や着色剤、赤外線吸収材料、電磁波遮蔽材料等として利用することが可能である。更に平板状金属粒子であるため、塗布することにより、基材水平面に対し、粒子を水平に並べることが可能である。 In the method for producing flat metal particles of the present invention, a triangular, hexagonal shape or the like is obtained by heating and reducing a metal compound such as silver nitrate or chloroauric acid together with polyvinylpyrrolidone (PVP) in a polyol compound such as ethylene glycol. The flat metal particles can be obtained. The obtained tabular metal particles have absorption derived from surface plasmon resonance from the visible range to the near infrared range, and show a vivid color development. Therefore, color materials such as inkjets and color filters, colorants, and infrared absorbing materials It can be used as an electromagnetic shielding material. Furthermore, since it is a flat metal particle, it is possible to arrange a particle | grain horizontally with respect to a base-material horizontal surface by apply | coating.
本発明によると、従来における問題を解決することができ、大量生産が可能であり、短時間で高濃度の平板状金属粒子を効率よく合成でき、安全かつ環境影響の少ない平板状金属粒子の製造方法及び該製造方法により製造された平板状金属粒子、並びに平板状金属粒子含有組成物、及び赤外線吸収材料を提供することができる。 According to the present invention, conventional problems can be solved, mass production is possible, high concentration flat metal particles can be efficiently synthesized in a short time, and production of flat metal particles that are safe and have little environmental impact. It is possible to provide a method, flat metal particles produced by the production method, a flat metal particle-containing composition, and an infrared absorbing material.
（平板状金属粒子の製造方法及び平板状金属粒子）
本発明の平板状金属粒子の製造方法は、ポリオール化合物を含む溶媒中に金属化合物及びピロリドン化合物を添加した反応液を、４０℃以上該溶媒の沸点以下の温度で加熱することにより、平板状金属粒子を製造する。
本発明の平板状金属粒子は、本発明の前記平板状金属粒子の製造方法により製造される。
以下、本発明の平板状金属粒子の製造方法の説明を通じて本発明の平板状金属粒子の詳細についても明らかにする。
(Manufacturing method of flat metal particles and flat metal particles)
In the method for producing flat metal particles of the present invention, a reaction liquid in which a metal compound and a pyrrolidone compound are added to a solvent containing a polyol compound is heated at a temperature not lower than 40 ° C. and not higher than the boiling point of the solvent. Producing particles.
The flat metal particles of the present invention are produced by the method for producing flat metal particles of the present invention.
Hereinafter, the details of the flat metal particles of the present invention will be clarified through the description of the method for producing flat metal particles of the present invention.
−溶媒−
前記溶媒としては、ポリオール化合物を３０体積％以上含むことが好ましく、４０体積％以上含むことがより好ましく、ポリオール化合物のみ（１００体積％）からなることが特に好ましい。前記ポリオール化合物の含有量が３０体積％未満であると、平板状金属粒子の収率が低くなってしまうことがある。
前記ポリオール化合物としては、水酸基を２つ以上有する化合物であれば特に制限はなく、目的に応じて適宜選択することができ、例えばエチレングリコール、ジエチレングリコール、トリエチレングリコール、プロピレングリコール、グリセリン、ポリエチレングリコール、などが挙げられる。これらは、１種単独で使用してもよいし、２種以上を併用してもよい。これらの中でも、エチレングリコールが特に好ましい。
前記ポリオール化合物以外の溶媒としては、特に制限はなく、目的に応じて適宜選択することができ、例えば水、ジメチルホルムアミド、ジメチルアセトアミドなどが挙げられる。
前記溶媒の沸点とは、溶媒に単位時間あたりに与える熱量を一定として温度上昇させる過程において、溶媒内部から気化が起り、溶媒全体から気泡が発生する状態で示す温度を最も長い時間保持する温度を意味する。
-Solvent-
The solvent preferably contains 30% by volume or more of the polyol compound, more preferably 40% by volume or more, and particularly preferably consists of only the polyol compound (100% by volume). If the content of the polyol compound is less than 30% by volume, the yield of the flat metal particles may be lowered.
The polyol compound is not particularly limited as long as it is a compound having two or more hydroxyl groups, and can be appropriately selected according to the purpose. For example, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, glycerin, polyethylene glycol, Etc. These may be used individually by 1 type and may use 2 or more types together. Among these, ethylene glycol is particularly preferable.
There is no restriction | limiting in particular as solvents other than the said polyol compound, According to the objective, it can select suitably, For example, water, dimethylformamide, dimethylacetamide etc. are mentioned.
The boiling point of the solvent is a temperature at which the temperature shown in a state where vaporization occurs from the inside of the solvent and bubbles are generated from the whole solvent in the process of raising the temperature with a constant amount of heat given to the solvent per unit time for the longest time. means.
−金属化合物−
前記金属化合物としては、例えば、金属塩、金属錯体、有機金属化合物などが挙げられる。
前記金属化合物における金属としては、例えば銀、金、白金、パラジウム、銅、ニッケル、コバルト、などが挙げられ、これらの中でも、銀、金が特に好ましい。
前記金属塩を形成する酸としては、無機酸及び有機酸のいずれであってもよい。
前記無機酸としては、特に制限はなく、目的に応じて適宜選択することができ、例えば硝酸；塩酸、臭化水素酸、ヨウ化水素酸等のハロゲン化水素酸などが挙げられる。
前記有機酸としては、特に制限はなく、目的に応じて適宜選択することができ、例えばカルボン酸、スルホン酸などが挙げられる。
前記カルボン酸としては、例えば酢酸、酪酸、シュウ酸、ステアリン酸、ベヘン酸、ラウリン酸、安息香酸などが挙げられる。
前記スルホン酸としては、例えばメチルスルホン酸などが挙げられる。
前記金属塩としては、例えば硝酸銀、塩化金酸、塩化白金酸などが挙げられる。
-Metal compounds-
Examples of the metal compound include metal salts, metal complexes, and organometallic compounds.
Examples of the metal in the metal compound include silver, gold, platinum, palladium, copper, nickel, and cobalt. Among these, silver and gold are particularly preferable.
The acid that forms the metal salt may be either an inorganic acid or an organic acid.
There is no restriction | limiting in particular as said inorganic acid, According to the objective, it can select suitably, For example, nitric acid; Hydrohalic acids, such as hydrochloric acid, hydrobromic acid, hydroiodic acid, etc. are mentioned.
There is no restriction | limiting in particular as said organic acid, According to the objective, it can select suitably, For example, carboxylic acid, a sulfonic acid, etc. are mentioned.
Examples of the carboxylic acid include acetic acid, butyric acid, oxalic acid, stearic acid, behenic acid, lauric acid, benzoic acid and the like.
Examples of the sulfonic acid include methyl sulfonic acid.
Examples of the metal salt include silver nitrate, chloroauric acid, and chloroplatinic acid.
前記金属錯体を形成するキレート剤としては、特に制限はなく、目的に応じて適宜選択することができ、例えばアセチルアセトナート、ＥＤＴＡなどが挙げられる。また、上記の金属塩と配位子とで錯体を形成してもよく、該配位子としては、例えばイミダゾール、ピリジン、フェニルメチルスルフィドなどが挙げられる。
なお、前記金属化合物には、金属イオンのハロゲン化錯体の酸（例えば塩化金酸、塩化白金酸など）、アルカリ金属塩（例えば塩化金酸ナトリウム、テトラクロロパラジウム酸ナトリウムなど）も含まれる。
There is no restriction | limiting in particular as a chelating agent which forms the said metal complex, According to the objective, it can select suitably, For example, acetylacetonate, EDTA, etc. are mentioned. Moreover, you may form a complex with said metal salt and a ligand, As this ligand, an imidazole, a pyridine, phenylmethyl sulfide etc. are mentioned, for example.
The metal compound includes an acid of a metal ion halide complex (for example, chloroauric acid, chloroplatinic acid and the like) and an alkali metal salt (for example, sodium chloroaurate and sodium tetrachloropalladate).
−ピロリドン化合物−
前記ピロリドン化合物としては、ポリビニルピロリドン（ＰＶＰ）、１−ビニル−２−ピロリドンなどが挙げられ、ポリビニルピロリドン（ＰＶＰ）が特に好ましい。
前記ポリビニルピロリドン（ＰＶＰ）は、ピロリドンユニットの繰り返し単位数が８５以上であることが好ましく、３００〜１２，０００がより好ましい。前記繰り返し単位数が８５未満であると、ＰＶＰが金属粒子の特定の結晶面に吸着できずに、球状粒子となってしまうとなることがある。
-Pyrrolidone compound-
Examples of the pyrrolidone compound include polyvinyl pyrrolidone (PVP) and 1-vinyl-2-pyrrolidone, and polyvinyl pyrrolidone (PVP) is particularly preferable.
In the polyvinyl pyrrolidone (PVP), the number of repeating units of pyrrolidone units is preferably 85 or more, and more preferably 300 to 12,000. If the number of repeating units is less than 85, PVP may not be adsorbed on a specific crystal plane of the metal particles and may become spherical particles.
本発明の平板状金属粒子の製造方法は、ポリオール化合物を含む溶媒中に金属化合物及びピロリドン化合物を添加した反応液を、４０℃以上（好ましくは５０℃以上）該溶媒の沸点以下の温度で０．１〜３時間加熱し、還元反応させて、平板状金属粒子を作製する。
前記加熱温度が４０℃未満であると、反応時間が長くかかりすぎてしまうことがある。
前記ピロリドン化合物のモル数（ユニット換算）と、前記金属化合物とのモル数の比（ピロリドン化合物／金属化合物）は、４以上が好ましく、５以上がより好ましい。前記モル比（ピロリドン化合物／金属化合物）が、４未満であると、球状粒子の比率が高くなってしまい、平板状金属粒子の収率が低くなってしまうことがある。
In the method for producing flat metal particles of the present invention, a reaction solution in which a metal compound and a pyrrolidone compound are added to a solvent containing a polyol compound is 0 ° C. or higher (preferably 50 ° C. or higher) at a temperature not higher than the boiling point of the solvent. . Heat for 1-3 hours to cause reduction reaction to produce flat metal particles.
If the heating temperature is less than 40 ° C, the reaction time may take too long.
The ratio of the number of moles of the pyrrolidone compound (unit conversion) to the number of moles of the metal compound (pyrrolidone compound / metal compound) is preferably 4 or more, and more preferably 5 or more. If the molar ratio (pyrrolidone compound / metal compound) is less than 4, the ratio of spherical particles may increase, and the yield of flat metal particles may decrease.
本発明の平板状金属粒子の製造方法により製造された平板状金属粒子は、可視域から近赤外域に表面プラズモン共鳴由来の吸収を有しており、鮮やかな発色を示すため、インクジェットやカラーフィルタ等の色材や着色剤、赤外線吸収材料、電磁波遮蔽材料等として利用することができる。 The tabular metal particles produced by the method for producing tabular metal particles of the present invention have absorption derived from surface plasmon resonance from the visible region to the near infrared region, and show a vivid color development. It can be used as a coloring material such as a coloring material, a colorant, an infrared ray absorbing material, an electromagnetic wave shielding material, and the like.
前記「平板状」とは、三角形、六角形、五角形等の形状をした板状の粒子であり、粒子径を粒子厚みで割った平均アスペクト比（粒子径／粒子厚み）が１．１以上（好ましくは２．０以上）である粒子を意味する。
前記粒子径は、１０ｎｍ〜１，０００ｎｍが好ましく、２０ｎｍ〜５００ｎｍがより好ましい。
前記平均アスペクト比（粒子径／粒子厚み）は、１．１以上が好ましく、１．１〜２０がより好ましく、２．０〜２０が更に好ましく、２．５〜１０が特に好ましく、３．０〜８．０が最も好ましい。
The “flat plate” is a plate-like particle having a triangular shape, a hexagonal shape, a pentagonal shape or the like, and an average aspect ratio (particle diameter / particle thickness) obtained by dividing the particle diameter by the particle thickness is 1.1 or more ( The particle is preferably 2.0 or more.
The particle diameter is preferably 10 nm to 1,000 nm, and more preferably 20 nm to 500 nm.
The average aspect ratio (particle diameter / particle thickness) is preferably 1.1 or more, more preferably 1.1 to 20, still more preferably 2.0 to 20, particularly preferably 2.5 to 10, -8.0 is most preferred.
ここで、前記平板状金属粒子の形状、粒子径、及び厚みの測定方法としては、以下の方法が挙げられる。
（１）粒子径の測定法
平板状金属粒子分散液をＴＥＭ観察用メッシュに滴下し、乾燥させた後、ＴＥＭで観察した結果、三角形や六角形状の粒子が観察された。図１に示すように観察された平板状金属粒子のＴＥＭ写真を画像処理することにより各粒子の円相当直径（同一面積の円で表したときの直径）を求め、求めた円相当直径を粒子径ａとした。
Here, the following methods are mentioned as a measuring method of the shape, particle diameter, and thickness of the said flat metal particle.
(1) Measuring method of particle diameter After dropping a flat metal particle dispersion liquid on a TEM observation mesh and drying it, as a result of observation by TEM, triangular or hexagonal particles were observed. The image of the TEM photograph of the flat metal particles observed as shown in FIG. 1 was used to determine the equivalent circle diameter of each particle (the diameter when represented by a circle of the same area). The diameter was a.
（２）厚みの測定法
平板状金属粒子厚みの測定法としては、ＴＥＭ観察による方法と、ＡＦＭによる方法がある。
・透過型電子顕微鏡（ＴＥＭ）観察
平板状金属粒子をエポキシ樹脂中に包埋した後、ミクロトームで粒子断面を含む切片を作製した。作製した切片をＴＥＭ観察用メッシュに載せ、ＴＥＭ観察を実施し、得られた写真から、粒子厚みｂを測定した。
・原子間力顕微鏡（ＡＦＭ）観察
平板状金属粒子分散液をシリコンウェハ上に滴下し、乾燥させた後、ＡＦＭで観察した三角形や六角形状の粒子について、図１に示すように横から見たＡＦＭ観察の段差測定による段差ｂを粒子厚みとして測定した。
上述のようにして求めた粒子径ａを粒子厚みｂで割った値を、アスペクト比＝ａ／ｂとして算出した。
(2) Thickness measurement method As a method for measuring the thickness of the flat metal particles, there are a method by TEM observation and a method by AFM.
-Observation with Transmission Electron Microscope (TEM) After embedding the flat metal particles in an epoxy resin, a section including a particle cross section was prepared with a microtome. The prepared slice was placed on a TEM observation mesh, TEM observation was performed, and the particle thickness b was measured from the obtained photograph.
Atomic force microscope (AFM) observation After dropping a flat metal particle dispersion onto a silicon wafer and drying, the triangular or hexagonal particles observed with AFM were viewed from the side as shown in FIG. The level difference b by the level difference measurement of AFM observation was measured as the particle thickness.
A value obtained by dividing the particle diameter a obtained as described above by the particle thickness b was calculated as aspect ratio = a / b.
本発明の平板状金属粒子の製造方法においては、少なくとも平板状金属粒子が作製できていればよく、製造される平板状金属粒子の生成率、即ち平板率は、２％以上が好ましく、５％以上がより好ましく、３０％以上が更に好ましく、５０％以上が特に好ましい。
前記平板率は、ＴＥＭで観察した結果、観察された平板状金属粒子２００個のうちの平板状金属粒子の割合を意味する。
In the method for producing tabular metal particles of the present invention, it is sufficient that at least the tabular metal particles can be produced. The production rate of the tabular metal particles to be produced, that is, the tabularity is preferably 2% or more, preferably 5%. The above is more preferable, 30% or more is further preferable, and 50% or more is particularly preferable.
The flat plate ratio means the ratio of the flat metal particles out of the 200 flat metal particles observed as a result of TEM observation.
（平板状金属粒子含有組成物）
本発明の平板状金属粒子含有組成物は、本発明の前記平板状金属粒子を含有し、更に必要に応じてその他の成分を含有してなる。
平均アスペクト比が１．１〜２０．０の前記平板状金属粒子を個数平均で３０％以上含有することが好ましい。
(Flat-shaped metal particle-containing composition)
The flat metal particle-containing composition of the present invention contains the flat metal particles of the present invention, and further contains other components as necessary.
The flat metal particles having an average aspect ratio of 1.1 to 20.0 are preferably contained in an average number of 30% or more.
前記その他の成分としては、例えば溶媒、分散剤などが挙げられる。
前記溶媒としては、特に制限はなく、目的に応じて適宜選択することができるが、例えば、水；メタノール、エタノール、ｎ−プロパノール、イソプロパノール、ｔ−ブチルアルコール、グリセリン、エチレングリコール、トリエチレングリコール、エチレングリコールモノメチルエーテル、ジエチレングリコールジメチルエーテル、プロピレングリコール、ジプロピレングリコール、２−メチル−２，４−ペンタンジオール等のアルコール系溶媒；アセトン、メチルエチルケトン（ＭＥＫ）、メチルイソブチルケトン、シクロヘキサノン、シクロペンタノン、２−ピロリドン、Ｎ−メチル−２−ピロリドン等のケトン系溶媒；酢酸エチル、酢酸ブチル等のエステル系溶媒；ジメチルホルムアミド、ジメチルアセトアミド等のアミド系溶媒；アセトニトリル、ブチロニトリル等のニトリル系溶媒；ジエチルエーテル、ジブチルエーテル、テトラヒドロフラン、ジオキサン等のエーテル系溶媒；クロロホルム、ジクロロメタン、四塩化炭素、ジクロロエタン、テトラクロロエタン、塩化メチレン、トリクロロエチレン、テトラクロロエチレン、クロロベンゼン、オルソジクロロベンゼン等のハロゲン化炭化水素類；フェノール、ｐ−クロロフェノール、ｏ−クロロフェノール、ｍ−クレゾール、ｏ−クレゾール、ｐ−クレゾール等のフェノール類；ベンゼン、トルエン、キシレン、メトキシベンゼン、１，２−ジメトキシベンゼン等の芳香族炭化水素類；二硫化炭素、エチルセルソルブ、ブチルセルソルブ、などが挙げられる。これらは、１種単独で使用してもよいし、２種以上を併用してもよい。
Examples of the other components include a solvent and a dispersant.
The solvent is not particularly limited and may be appropriately selected depending on the intended purpose. For example, water; methanol, ethanol, n-propanol, isopropanol, t-butyl alcohol, glycerin, ethylene glycol, triethylene glycol, Alcohol solvents such as ethylene glycol monomethyl ether, diethylene glycol dimethyl ether, propylene glycol, dipropylene glycol, 2-methyl-2,4-pentanediol; acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone, cyclohexanone, cyclopentanone, 2- Ketone solvents such as pyrrolidone and N-methyl-2-pyrrolidone; ester solvents such as ethyl acetate and butyl acetate; amide solvents such as dimethylformamide and dimethylacetamide; Nitrile solvents such as cetonitrile and butyronitrile; ether solvents such as diethyl ether, dibutyl ether, tetrahydrofuran, and dioxane; chloroform, dichloromethane, carbon tetrachloride, dichloroethane, tetrachloroethane, methylene chloride, trichloroethylene, tetrachloroethylene, chlorobenzene, orthodichlorobenzene, etc. Halogenated hydrocarbons; phenols such as phenol, p-chlorophenol, o-chlorophenol, m-cresol, o-cresol, p-cresol; benzene, toluene, xylene, methoxybenzene, 1,2-dimethoxybenzene, etc. Aromatic hydrocarbons; carbon disulfide, ethyl cellosolve, butyl cellosolve, and the like. These may be used individually by 1 type and may use 2 or more types together.
本発明の平板状金属粒子含有組成物は、本発明の前記平板状金属粒子を含有してなり、例えば赤外線吸収材料、光学フィルタ、配線材料、電極材料、触媒、着色剤、インクジェット用インク、カラーフィルタ用色材、フィルタ、化粧料、偽造防止用インク、電磁波遮蔽膜、表面増強蛍光センサ、表面増強ラマン散乱センサ、生体用マーカー、記録材料、ドラッグデリバリー用薬物担体、バイオセンサ、ＤＮＡチップ、検査薬などの種々の用途に用いることができるが、以下の赤外線吸収材料として特に好適に用いられる。 The flat metal particle-containing composition of the present invention contains the flat metal particles of the present invention, and includes, for example, an infrared absorbing material, an optical filter, a wiring material, an electrode material, a catalyst, a colorant, an inkjet ink, and a color. Coloring materials for filters, filters, cosmetics, anti-counterfeiting inks, electromagnetic shielding films, surface-enhanced fluorescence sensors, surface-enhanced Raman scattering sensors, biomarkers, recording materials, drug delivery drug carriers, biosensors, DNA chips, inspection Although it can be used for various uses such as medicine, it is particularly suitably used as the following infrared absorbing material.
（赤外線吸収材料）
本発明の赤外線吸収材料は、本発明の前記平板状金属粒子含有組成物からなる赤外線吸収層を有してなり、基材、下塗り層、オーバーコート層、更に必要に応じてその他の層を有してなる。
(Infrared absorbing material)
The infrared absorbing material of the present invention has an infrared absorbing layer made of the above-mentioned composition containing flat metal particles of the present invention, and has a substrate, an undercoat layer, an overcoat layer, and other layers as necessary. Do it.
−近赤外線吸収フィルター−
近赤外線とは、約７００ｎｍ〜２，２００ｎｍの電磁波であり、近赤外線吸収フィルターとは、約７００ｎｍ〜２，２００ｎｍの電磁波を吸収する材料を含むフィルターのことをいう。例えばプラズマディスプレイパネルでは、キセノンの紫外線発光により蛍光体を励起しているが、キセノンは、紫外光だけでなく、８２３ｎｍ、８８２ｎｍ、９１６ｎｍ、９８０ｎｍ付近の近赤外線領域にも強い発光を示す。キセノン発光に伴う８００ｎｍ〜１０００ｎｍの近赤外線は、テレビ、エアコン等の家庭用電化製品のリモコン動作不良やワイヤレスマイクの動作不良の原因になるため、遮蔽する近赤外線フィルターが必要である。また近赤外線は熱線であるため、熱線遮蔽の効果もある。
本発明の平板状金属粒子はいずれも近赤外線の吸収を示すものの、光吸収効率や吸収波長は粒子形状によって変化することが分かっており、近赤外線の吸収用途として好ましい平板状銀粒子の平均アスペクト比は、２．５〜１０．０が好ましく、近赤外線の吸収に好ましい平板状銀粒子の粒子径は、２０ｎｍ〜１，０００ｎｍである。
-Near-infrared absorption filter-
Near-infrared rays are electromagnetic waves of about 700 nm to 2,200 nm, and near-infrared absorption filters are filters containing a material that absorbs electromagnetic waves of about 700 nm to 2,200 nm. For example, in a plasma display panel, a phosphor is excited by ultraviolet light emission of xenon, but xenon exhibits strong light emission not only in ultraviolet light but also in a near infrared region near 823 nm, 882 nm, 916 nm, and 980 nm. Near-infrared rays of 800 nm to 1000 nm accompanying xenon emission cause malfunctions in remote control of home electric appliances such as televisions and air conditioners and malfunctions of wireless microphones. Therefore, a near-infrared filter for shielding is necessary. Moreover, since near infrared rays are heat rays, they also have a heat ray shielding effect.
Although the tabular metal particles of the present invention all exhibit near-infrared absorption, it is known that the light absorption efficiency and the absorption wavelength vary depending on the particle shape, and the average aspect ratio of tabular silver particles preferred for near-infrared absorption applications The ratio is preferably 2.5 to 10.0, and the preferred particle size of tabular silver particles for near infrared absorption is 20 nm to 1,000 nm.
−赤外線吸収層−
前記赤外線吸収層は、本発明の前記平板状金属粒子含有組成物からなる。
前記赤外線吸収層は、本発明の前記平板状金属粒子含有組成物を基材上に塗布して、形成することができる。
前記塗布方法としては、例えば、スピンコート法、キャスト法、ロールコート法、フローコート法、プリント法、ディップコート法、流延成膜法、バーコート法、グラビア印刷法などが挙げられる。
前記赤外線吸収層の厚みは、特に制限はなく、目的に応じて適宜選択することができ、０．０１μｍ〜１００μｍが好ましい。
-Infrared absorbing layer-
The infrared absorbing layer is composed of the flat metal particle-containing composition of the present invention.
The infrared absorption layer can be formed by applying the flat metal particle-containing composition of the present invention on a substrate.
Examples of the coating method include spin coating, casting, roll coating, flow coating, printing, dip coating, casting film formation, bar coating, and gravure printing.
There is no restriction | limiting in particular in the thickness of the said infrared absorption layer, According to the objective, it can select suitably, 0.01 micrometer-100 micrometers are preferable.
−基材−
前記基材としては、その形状、構造、大きさ等については、特に制限はなく、目的に応じて適宜選択することができ、前記形状としては、例えば平板状、シート状、フィルム状などが挙げられ、前記構造としては、例えば単層構造であってもいし、積層構造であってもよく適宜選択することができる。
前記基材の材料としては、特に制限はなく、無機材料及び有機材料のいずれであっても好適に用いることができる。
前記無機材料としては、例えば、ガラス、石英、シリコンなどが挙げられる。
前記有機材料としては、例えば、トリアセチルセルロース（ＴＡＣ）等のアセテート系樹脂；ポリエチレンテレフタレート（ＰＥＴ）等のポリエステル系樹脂；ポリエーテルスルホン系樹脂、ポリスルホン系樹脂、ポリカーボネート系樹脂、ポリアミド系樹脂、ポリイミド系樹脂、ポリオレフィン系樹脂、アクリル系樹脂、ポリノルボルネン系樹脂、セルロース系樹脂、ポリアリレート系樹脂、ポリスチレン系樹脂、ポリビニルアルコール系樹脂、ポリ塩化ビニル系樹脂、ポリ塩化ビニリデン系樹脂、ポリアクリル系樹脂、などが挙げられる。これらは、１種単独で使用してもよいし、２種以上を併用してもよい。
-Base material-
The shape, structure, size and the like of the substrate are not particularly limited and can be appropriately selected according to the purpose. Examples of the shape include a plate shape, a sheet shape, and a film shape. For example, the structure may be a single layer structure or a laminated structure, and can be appropriately selected.
There is no restriction | limiting in particular as a material of the said base material, Any of an inorganic material and an organic material can be used conveniently.
Examples of the inorganic material include glass, quartz, and silicon.
Examples of the organic material include acetate resins such as triacetyl cellulose (TAC); polyester resins such as polyethylene terephthalate (PET); polyethersulfone resins, polysulfone resins, polycarbonate resins, polyamide resins, polyimides Resin, polyolefin resin, acrylic resin, polynorbornene resin, cellulose resin, polyarylate resin, polystyrene resin, polyvinyl alcohol resin, polyvinyl chloride resin, polyvinylidene chloride resin, polyacrylic resin , Etc. These may be used individually by 1 type and may use 2 or more types together.
本発明の赤外線吸収材料は、赤外線遮蔽性に優れているので、赤外線遮蔽フィルタとして、例えばプラズマディスプレイ表示装置、ＥＬ表示装置、ＣＲＴ表示装置、液晶表示装置等の表示装置などに好適に用いられる。 Since the infrared absorbing material of the present invention is excellent in infrared shielding properties, it is suitably used as an infrared shielding filter for display devices such as plasma display devices, EL display devices, CRT display devices, and liquid crystal display devices.
以下、本発明の実施例を説明するが、本発明は、これらの実施例に何ら限定されるものではない。 Examples of the present invention will be described below, but the present invention is not limited to these examples.
（実施例１）
−銀粒子の作製−
表１−１及び表１−２に示すように、５０ｍＭの硝酸銀（関東化学株式会社製）のエチレングリコール溶液１５ｍＬに、２５０ｍＭのポリビニルピロリドン（ＰＶＰ）（Ｋ３０、質量平均分子量４０，０００）のエチレングリコール溶液１５ｍＬを添加した。この反応液をホットスターラーで、１３０℃にて１時間加熱して攪拌したところ、反応液の色が無色から青色に変化した。この反応液を冷却した後、水で５倍希釈し、遠心分離（１０，５００ｒｐｍ×３０分）により精製することにより、平板状銀粒子分散液を作製した。
得られた平板状銀粒子分散液を透過型電子顕微鏡（ＴＥＭ；日本電子株式会社製、１２００ＥＸ）観察用のグリッドに載せ、乾燥させた後にＴＥＭ観察を行ったところ、図５に示す、主に平板状の三角形及び六角形の銀粒子が確認された。また、ＴＥＭ観察の結果、観察された銀粒子２００個のうち、５０％以上が平板状銀粒子であった。
Example 1
-Production of silver particles-
As shown in Table 1-1 and Table 1-2, ethylene of 250 mM polyvinylpyrrolidone (PVP) (K30, mass average molecular weight 40,000) was added to 15 mL of an ethylene glycol solution of 50 mM silver nitrate (manufactured by Kanto Chemical Co., Inc.). 15 mL of glycol solution was added. When this reaction solution was stirred with a hot stirrer at 130 ° C. for 1 hour, the color of the reaction solution changed from colorless to blue. The reaction solution was cooled, diluted 5 times with water, and purified by centrifugation (10,500 rpm × 30 minutes) to prepare a tabular silver particle dispersion.
The obtained tabular silver particle dispersion was placed on a transmission electron microscope (TEM; manufactured by JEOL Ltd., 1200EX) observation grid, dried, and then subjected to TEM observation. As shown in FIG. Flat triangular and hexagonal silver particles were observed. As a result of TEM observation, 50% or more of the 200 silver particles observed were tabular silver particles.
（実施例２）
−銀粒子の作製−
実施例１において、ＰＶＰ濃度を２５０ｍＭから６００ｍＭに変えた以外は、実施例１と同様にして、実施例２の平板状銀粒子分散液を作製した。
得られた平板状銀粒子分散液を実施例１と同様にしてＴＥＭ観察を行ったところ、図６に示す、主に平板状の三角形及び六角形の銀粒子が確認された。また、ＴＥＭ観察の結果、観察された銀粒子２００個のうち、５０％以上が平板状銀粒子であった。
(Example 2)
-Production of silver particles-
A tabular silver particle dispersion of Example 2 was prepared in the same manner as in Example 1 except that the PVP concentration was changed from 250 mM to 600 mM in Example 1.
The obtained tabular silver particle dispersion was subjected to TEM observation in the same manner as in Example 1. As a result, mainly tabular triangular and hexagonal silver particles shown in FIG. 6 were confirmed. As a result of TEM observation, 50% or more of the 200 silver particles observed were tabular silver particles.
（実施例３）
−銀粒子の作製−
実施例１において、ＰＶＰ濃度を２５０ｍＭから８００ｍＭに変えた以外は、実施例１と同様にして、実施例２の平板状銀粒子分散液を作製した。
得られた平板状銀粒子分散液を実施例１と同様にしてＴＥＭ観察を行ったところ、図７に示す、主に平板状の三角形及び六角形の銀粒子が確認された。また、ＴＥＭ観察の結果、観察された銀粒子２００個のうち、５０％以上が平板状銀粒子であった。
(Example 3)
-Production of silver particles-
A tabular silver particle dispersion of Example 2 was produced in the same manner as in Example 1 except that the PVP concentration was changed from 250 mM to 800 mM in Example 1.
The obtained tabular silver particle dispersion was subjected to TEM observation in the same manner as in Example 1. As a result, mainly tabular triangular and hexagonal silver particles shown in FIG. 7 were confirmed. As a result of TEM observation, 50% or more of the 200 silver particles observed were tabular silver particles.
（実施例４）
−銀粒子の作製−
実施例１において、ＰＶＰ濃度を２５０ｍＭから２５ｍＭに変えた以外は、実施例１と同様にして、実施例４の銀粒子分散液を作製した。
得られた銀粒子分散液を実施例１と同様にしてＴＥＭ観察を行ったところ、図３に示す、主に球状の銀粒子が確認された。また、ＴＥＭ観察の結果、観察された銀粒子２００個のうち、５％が平板状銀粒子であった。
Example 4
-Production of silver particles-
In Example 1, the silver particle dispersion liquid of Example 4 was produced like Example 1 except having changed the PVP density | concentration from 250 mM to 25 mM.
The obtained silver particle dispersion was subjected to TEM observation in the same manner as in Example 1. As a result, mainly spherical silver particles shown in FIG. 3 were confirmed. As a result of TEM observation, 5% of the 200 silver particles observed were tabular silver particles.
（実施例５）
−銀粒子の作製−
実施例１において、ＰＶＰ濃度を２５０ｍＭから５０ｍＭに変えた以外は、実施例１と同様にして、実施例５の銀粒子分散液を作製した。
得られた銀粒子分散液を実施例１と同様にしてＴＥＭ観察を行ったところ、図４に示す、主に球状の銀粒子が確認された。また、ＴＥＭ観察の結果、観察された銀粒子２００個のうち、１０％が平板状銀粒子であった。
(Example 5)
-Production of silver particles-
In Example 1, the silver particle dispersion liquid of Example 5 was produced like Example 1 except having changed the PVP density | concentration from 250 mM to 50 mM.
When the obtained silver particle dispersion was subjected to TEM observation in the same manner as in Example 1, mainly spherical silver particles shown in FIG. 4 were confirmed. As a result of TEM observation, 10% of the 200 silver particles observed were tabular silver particles.
（実施例６）
−銀粒子の作製−
実施例１において、ＰＶＰ濃度を２５０ｍＭから１００ｍＭに変えた以外は、実施例１と同様にして、実施例６の銀粒子分散液を作製した。
得られた銀粒子分散液を実施例１と同様にしてＴＥＭ観察を行ったところ、主に球状の銀粒子が確認された。また、ＴＥＭ観察の結果、観察された銀粒子２００個のうち、１８％が平板状銀粒子であった。
(Example 6)
-Production of silver particles-
In Example 1, the silver particle dispersion liquid of Example 6 was produced like Example 1 except having changed the PVP density | concentration from 250 mM to 100 mM.
When the obtained silver particle dispersion was subjected to TEM observation in the same manner as in Example 1, spherical silver particles were mainly confirmed. As a result of TEM observation, 18% of the 200 silver particles observed were tabular silver particles.
（実施例７）
−銀粒子の作製−
実施例１において、ＰＶＰ濃度を２５０ｍＭから２００ｍＭに変えた以外は、実施例１と同様にして、実施例７の平板状銀粒子分散液を作製した。
得られた平板状銀粒子分散液を実施例１と同様にしてＴＥＭ観察を行ったところ、主に平板状の三角形及び六角形の銀粒子が確認された。また、ＴＥＭ観察の結果、観察された銀粒子２００個のうち、３２％が平板状銀粒子であった。
(Example 7)
-Production of silver particles-
A tabular silver particle dispersion of Example 7 was prepared in the same manner as in Example 1 except that the PVP concentration was changed from 250 mM to 200 mM in Example 1.
When the obtained tabular silver particle dispersion was subjected to TEM observation in the same manner as in Example 1, mainly tabular triangular and hexagonal silver particles were confirmed. As a result of TEM observation, 32% of the 200 silver particles observed were tabular silver particles.
（実施例８）
−銀粒子の作製−
実施例１において、ＰＶＰ濃度を２５０ｍＭから１０００ｍＭに変えた以外は、実施例１と同様にして、実施例８の平板状銀粒子分散液を作製した。
得られた平板状銀粒子分散液を実施例１と同様にしてＴＥＭ観察を行ったところ、主に平板状の三角形及び六角形の銀粒子が確認された。また、ＴＥＭ観察の結果、観察された銀粒子２００個のうち、５０％以上が平板状銀粒子であった。
(Example 8)
-Production of silver particles-
A tabular silver particle dispersion of Example 8 was prepared in the same manner as in Example 1 except that the PVP concentration was changed from 250 mM to 1000 mM in Example 1.
When the obtained tabular silver particle dispersion was subjected to TEM observation in the same manner as in Example 1, mainly tabular triangular and hexagonal silver particles were confirmed. As a result of TEM observation, 50% or more of the 200 silver particles observed were tabular silver particles.
（実施例９）
−銀粒子の作製−
実施例１において、ポリビニルピロリドン（ＰＶＰ）（Ｋ３０、質量平均分子量４０，０００）２５０ｍＭを、１−ビニル−２−ピロリドン６００ｍＭに変えた以外は、実施例１と同様にして、実施例９の銀粒子を作製した。
得られた銀粒子分散液を実施例１と同様にしてＴＥＭ観察を行ったところ、主に球状の銀粒子が確認された。また、ＴＥＭ観察の結果、観察された銀粒子２００個のうち、４％が平板状銀粒子であった。
Example 9
-Production of silver particles-
The silver of Example 9 was obtained in the same manner as in Example 1 except that 250 mM polyvinylpyrrolidone (PVP) (K30, mass average molecular weight 40,000) 250 mM was changed to 1-vinyl-2-pyrrolidone 600 mM. Particles were made.
When the obtained silver particle dispersion was subjected to TEM observation in the same manner as in Example 1, spherical silver particles were mainly confirmed. As a result of TEM observation, 4% of the observed 200 silver particles were tabular silver particles.
（実施例１０）
−銀粒子の作製−
実施例１において、ポリビニルピロリドン（ＰＶＰ）（Ｋ３０、質量平均分子量４０，０００）を、ＰＶＰ（質量平均分子量＝１０，０００、Ｋ１５）に変えた以外は、実施例１と同様にして、実施例１０の平板状銀粒子分散液を作製した。
得られた平板状銀粒子分散液を実施例１と同様にしてＴＥＭ観察を行ったところ、主に平板状の三角形及び六角形の銀粒子が確認された。また、ＴＥＭ観察の結果、観察された銀粒子２００個のうち、５０％以上が平板状銀粒子であった。
(Example 10)
-Production of silver particles-
In Example 1, polyvinyl pyrrolidone (PVP) (K30, mass average molecular weight 40,000) was changed to PVP (mass average molecular weight = 10,000, K15). Ten tabular silver particle dispersions were prepared.
When the obtained tabular silver particle dispersion was subjected to TEM observation in the same manner as in Example 1, mainly tabular triangular and hexagonal silver particles were confirmed. As a result of TEM observation, 50% or more of the 200 silver particles observed were tabular silver particles.
（実施例１１）
−銀粒子の作製−
実施例１において、ポリビニルピロリドン（ＰＶＰ）（Ｋ３０、質量平均分子量４０，０００）を、ポリビニルピロリドン（ＰＶＰ）（質量平均分子量＝３６０，０００、Ｋ９０）に変えた以外は、実施例１と同様にして、実施例１１の平板状銀粒子分散液を作製した。
得られた平板状銀粒子分散液を実施例１と同様にしてＴＥＭ観察を行ったところ、主に平板状の三角形及び六角形の銀粒子が確認された。また、ＴＥＭ観察の結果、観察された銀粒子２００個のうち、５０％以上が平板状銀粒子であった。
(Example 11)
-Production of silver particles-
In Example 1, polyvinyl pyrrolidone (PVP) (K30, mass average molecular weight 40,000) was changed to polyvinyl pyrrolidone (PVP) (mass average molecular weight = 360,000, K90). Thus, a tabular silver particle dispersion of Example 11 was prepared.
When the obtained tabular silver particle dispersion was subjected to TEM observation in the same manner as in Example 1, mainly tabular triangular and hexagonal silver particles were confirmed. As a result of TEM observation, 50% or more of the 200 silver particles observed were tabular silver particles.
（実施例１２）
−銀粒子の作製−
実施例１において、反応温度を１３０℃から４０℃に変えた以外は、実施例１と同様にして、実施例１２の銀粒子分散液を作製した。
得られた銀粒子分散液を実施例１と同様にしてＴＥＭ観察を行ったところ、主に球状の銀粒子が確認された。また、ＴＥＭ観察の結果、観察された銀粒子２００個のうち、２％が平板状銀粒子であった。
Example 12
-Production of silver particles-
A silver particle dispersion of Example 12 was prepared in the same manner as in Example 1 except that the reaction temperature was changed from 130 ° C. to 40 ° C. in Example 1.
When the obtained silver particle dispersion was subjected to TEM observation in the same manner as in Example 1, spherical silver particles were mainly confirmed. As a result of TEM observation, 2% of the 200 silver particles observed were tabular silver particles.
（実施例１３）
−銀粒子の作製−
実施例１において、反応温度を１３０℃から１８５℃に変えた以外は、実施例１と同様にして、実施例１３の平板状銀粒子分散液を作製した。
得られた平板状銀粒子分散液を実施例１と同様にしてＴＥＭ観察を行ったところ、主に平板状の三角形及び六角形の銀粒子が確認された。また、ＴＥＭ観察の結果、観察された銀粒子２００個のうち、５０％以上が平板状銀粒子であった。
(Example 13)
-Production of silver particles-
A tabular silver particle dispersion of Example 13 was prepared in the same manner as in Example 1 except that the reaction temperature was changed from 130 ° C. to 185 ° C. in Example 1.
When the obtained tabular silver particle dispersion was subjected to TEM observation in the same manner as in Example 1, mainly tabular triangular and hexagonal silver particles were confirmed. As a result of TEM observation, 50% or more of the 200 silver particles observed were tabular silver particles.
（実施例１４）
−銀粒子の作製−
実施例１において、ポリオール化合物としてのエチレングリコールを、ジエチレングリコールに変えた以外は、実施例１と同様にして、実施例１４の平板状銀粒子分散液を作製した。
得られた平板状銀粒子分散液を実施例１と同様にしてＴＥＭ観察を行ったところ、主に平板状の三角形及び六角形の銀粒子が確認された。また、ＴＥＭ観察の結果、観察された銀粒子２００個のうち、５０％以上が平板状銀粒子であった。
(Example 14)
-Production of silver particles-
A tabular silver particle dispersion of Example 14 was prepared in the same manner as in Example 1 except that ethylene glycol as the polyol compound was changed to diethylene glycol in Example 1.
When the obtained tabular silver particle dispersion was subjected to TEM observation in the same manner as in Example 1, mainly tabular triangular and hexagonal silver particles were confirmed. As a result of TEM observation, 50% or more of the 200 silver particles observed were tabular silver particles.
（実施例１５）
−銀粒子の作製−
実施例１において、ポリオール化合物としてのエチレングリコールを、トリエチレングリコールに変えた以外は、実施例１と同様にして、実施例１５の平板状銀粒子分散液を作製した。
得られた平板状銀粒子分散液を実施例１と同様にしてＴＥＭ観察を行ったところ、主に平板状の三角形及び六角形の銀粒子が確認された。また、ＴＥＭ観察の結果、観察された銀粒子２００個のうち、５０％以上が平板状銀粒子であった。
(Example 15)
-Production of silver particles-
A tabular silver particle dispersion of Example 15 was prepared in the same manner as in Example 1 except that ethylene glycol as the polyol compound was changed to triethylene glycol in Example 1.
When the obtained tabular silver particle dispersion was subjected to TEM observation in the same manner as in Example 1, mainly tabular triangular and hexagonal silver particles were confirmed. As a result of TEM observation, 50% or more of the 200 silver particles observed were tabular silver particles.
（実施例１６）
−金粒子の作製−
実施例１において、金属化合物としての硝酸銀を、塩化金酸に変え、ＰＶＰ濃度を２５０ｍＭから２００ｍＭに変えた以外は、実施例１と同様にして、実施例１６の平板状金粒子分散液を作製した。
得られた平板状金粒子分散液を実施例１と同様にしてＴＥＭ観察を行ったところ、主に平板状の三角形及び六角形の金粒子が確認された。また、ＴＥＭ観察の結果、観察された銀粒子２００個のうち、３８％が平板状金粒子であった。
(Example 16)
-Production of gold particles-
In Example 1, except that silver nitrate as a metal compound was changed to chloroauric acid and the PVP concentration was changed from 250 mM to 200 mM, a plate-like gold particle dispersion of Example 16 was prepared in the same manner as in Example 1. did.
The obtained tabular gold particle dispersion was subjected to TEM observation in the same manner as in Example 1. As a result, mainly tabular triangular and hexagonal gold particles were confirmed. As a result of TEM observation, 38% of the 200 silver particles observed were flat gold particles.
（実施例１７）
−金粒子の作製−
実施例１において、金属化合物を硝酸銀から塩化金酸に変えた以外は、実施例１と同様にして、実施例１７の平板状金粒子分散液を作製した。
得られた平板状金粒子分散液を実施例１と同様にしてＴＥＭ観察を行ったところ、主に平板状の三角形及び六角形の金粒子が確認された。また、ＴＥＭ観察の結果、観察された銀粒子２００個のうち、５０％以上が平板状金粒子であった。
(Example 17)
-Production of gold particles-
A tabular gold particle dispersion of Example 17 was prepared in the same manner as in Example 1 except that the metal compound was changed from silver nitrate to chloroauric acid in Example 1.
The obtained tabular gold particle dispersion was subjected to TEM observation in the same manner as in Example 1. As a result, mainly tabular triangular and hexagonal gold particles were confirmed. As a result of TEM observation, 50% or more of the 200 silver particles observed were flat gold particles.
（実施例１８）
−金粒子の作製−
実施例１において、金属化合物を硝酸銀から塩化金酸に変え、ＰＶＰ濃度を２５０ｍＭから６００ｍＭに変えた以外は、実施例１と同様にして、実施例１８の平板状金粒子分散液を作製した。
得られた平板状金粒子分散液を実施例１と同様にしてＴＥＭ観察を行ったところ、主に平板状の三角形及び六角形の金粒子が確認された。また、ＴＥＭ観察の結果、観察された金粒子２００個のうち、５０％以上が平板状金粒子であった。
(Example 18)
-Production of gold particles-
A tabular gold particle dispersion of Example 18 was prepared in the same manner as in Example 1 except that the metal compound was changed from silver nitrate to chloroauric acid and the PVP concentration was changed from 250 mM to 600 mM in Example 1.
The obtained tabular gold particle dispersion was subjected to TEM observation in the same manner as in Example 1. As a result, mainly tabular triangular and hexagonal gold particles were confirmed. As a result of TEM observation, 50% or more of the 200 gold particles observed were tabular gold particles.
（実施例１９）
−白金粒子の作製−
実施例１において、金属化合物としての硝酸銀を、塩化白金酸に変えた以外は、実施例１と同様にして、実施例１９の平板状白金粒子分散液を作製した。
得られた平板状金粒子分散液を実施例１と同様にしてＴＥＭ観察を行ったところ、主に平板状の三角形及び六角形の金粒子が確認された。また、ＴＥＭ観察の結果、観察された金粒子２００個のうち、５０％以上が平板状金粒子であった。
Example 19
-Production of platinum particles-
In Example 1, a plate-like platinum particle dispersion of Example 19 was prepared in the same manner as in Example 1 except that silver nitrate as the metal compound was changed to chloroplatinic acid.
The obtained tabular gold particle dispersion was subjected to TEM observation in the same manner as in Example 1. As a result, mainly tabular triangular and hexagonal gold particles were confirmed. As a result of TEM observation, 50% or more of the 200 gold particles observed were tabular gold particles.
（実施例２０）
−パラジウム粒子の作製−
実施例１において、金属化合物としての硝酸銀を、塩化パラジウムに変えた以外は、実施例１と同様にして、実施例２０の平板状パラジウム粒子分散液を作製した。
得られた平板状パラジウム粒子分散液を実施例１と同様にしてＴＥＭ観察を行ったところ、主に平板状の三角形及び六角形のパラジウム粒子が確認された。また、ＴＥＭ観察の結果、観察された金粒子２００個のうち、５０％以上が平板状パラジウム粒子であった。
(Example 20)
-Preparation of palladium particles-
In Example 1, a plate-like palladium particle dispersion of Example 20 was produced in the same manner as in Example 1 except that silver nitrate as the metal compound was changed to palladium chloride.
When the obtained flat palladium particle dispersion was subjected to TEM observation in the same manner as in Example 1, mainly flat triangular and hexagonal palladium particles were confirmed. As a result of TEM observation, 50% or more of the 200 gold particles observed were tabular palladium particles.
（実施例２１）
−銀粒子の作製−
実施例１において、溶媒中のポリオール化合物としてのエチレングリコールの比率を３０体積％（水７０体積％）に変えた以外は、実施例１と同様にして、実施例２１の平板状銀粒子分散液を作製した。
得られた平板状銀粒子分散液を実施例１と同様にしてＴＥＭ観察を行ったところ、主に平板状の三角形及び六角形の銀粒子が確認された。また、ＴＥＭ観察の結果、観察された金粒子２００個のうち、３２％が平板状銀粒子であった。
(Example 21)
-Production of silver particles-
The tabular silver particle dispersion liquid of Example 21 was obtained in the same manner as in Example 1 except that the ratio of ethylene glycol as a polyol compound in the solvent was changed to 30% by volume (70% by volume of water). Was made.
When the obtained tabular silver particle dispersion was subjected to TEM observation in the same manner as in Example 1, mainly tabular triangular and hexagonal silver particles were confirmed. As a result of TEM observation, 32% of the 200 gold particles observed were tabular silver particles.
（実施例２２）
−銀粒子の作製−
実施例１において、溶媒中のポリオール化合物としてのエチレングリコールの比率を１５体積％（水８５体積％）に変えた以外は、実施例１と同様にして、実施例２２の銀粒子分散液を作製した。
得られた銀粒子分散液を実施例１と同様にしてＴＥＭ観察を行ったところ、主に球状の銀粒子が確認された。また、ＴＥＭ観察の結果、観察された銀粒子２００個のうち、１５％が平板状銀粒子であった。
(Example 22)
-Production of silver particles-
In Example 1, the silver particle dispersion of Example 22 was prepared in the same manner as in Example 1 except that the ratio of ethylene glycol as the polyol compound in the solvent was changed to 15% by volume (85% by volume of water). did.
When the obtained silver particle dispersion was subjected to TEM observation in the same manner as in Example 1, spherical silver particles were mainly confirmed. As a result of TEM observation, 15% of the 200 silver particles observed were tabular silver particles.
（実施例２３）
−銀粒子の作製−
実施例１において、溶媒中のポリオール化合物としてのエチレングリコールの比率を５体積％（水９５体積％）に変えた以外は、実施例１と同様にして、実施例２３の銀粒子分散液を作製した。
得られた銀粒子分散液を実施例１と同様にしてＴＥＭ観察を行ったところ、主に球状の銀粒子が確認された。また、ＴＥＭ観察の結果、観察された銀粒子２００個のうち、１１％が平板状銀粒子であった。
(Example 23)
-Production of silver particles-
In Example 1, the silver particle dispersion of Example 23 was prepared in the same manner as in Example 1 except that the ratio of ethylene glycol as the polyol compound in the solvent was changed to 5% by volume (95% by volume of water). did.
When the obtained silver particle dispersion was subjected to TEM observation in the same manner as in Example 1, spherical silver particles were mainly confirmed. As a result of TEM observation, 11% of the 200 silver particles observed were tabular silver particles.
（比較例１）
−銀粒子の作製−
表１−１及び表１−２に示すように、Ｎａｎｏ Ｌｅｔｔ ．２， ９０３−９０５（２００２）（非特許文献３）に記載の方法にしたがって、比較例１の平板状銀粒子分散液を作製した。
得られた平板状銀粒子分散液を実施例１と同様にしてＴＥＭ観察を行ったところ、主に平板状の三角形及び六角形の銀粒子が確認された。また、ＴＥＭ観察の結果、観察された金粒子２００個のうち、４５％が平板状銀粒子であった。
(Comparative Example 1)
-Production of silver particles-
As shown in Table 1-1 and Table 1-2, Nano Lett. 2, 903-905 (2002) (non-patent document 3), a tabular silver particle dispersion of Comparative Example 1 was prepared.
When the obtained tabular silver particle dispersion was subjected to TEM observation in the same manner as in Example 1, mainly tabular triangular and hexagonal silver particles were confirmed. As a result of TEM observation, 45% of the 200 gold particles observed were tabular silver particles.
（比較例２）
−銀粒子の作製−
表１−１及び表１−２に示すように、特開２００７−１３８２４９号公報の実施例１に記載の方法にしたがって、比較例２の平板状銀粒子分散液を作製した。
得られた平板状銀粒子分散液を実施例１と同様にしてＴＥＭ観察を行ったところ、主に平板状の三角形及び六角形の銀粒子が確認された。また、ＴＥＭ観察の結果、観察された金粒子２００個のうち、４２％が平板状銀粒子であった。
(Comparative Example 2)
-Production of silver particles-
As shown in Table 1-1 and Table 1-2, a tabular silver particle dispersion of Comparative Example 2 was prepared according to the method described in Example 1 of JP-A-2007-138249.
When the obtained tabular silver particle dispersion was subjected to TEM observation in the same manner as in Example 1, mainly tabular triangular and hexagonal silver particles were confirmed. As a result of TEM observation, 42% of the 200 gold particles observed were tabular silver particles.
次に、実施例１〜５の各銀粒子分散液を水で１０倍に希釈し、日本分光株式会社製の紫外・可視分光器Ｖ−５６０により分光スペクトルを測定した。結果を図２に示す。
図２の結果から、平均アスペクト比が１．５より大きく、また平板状銀粒子を５０％以上含有する実施例１〜３は、主な生成物が平均アスペクト比の小さな球状銀粒子である実施例４〜５には見られない長波側の吸収が認められた。
Next, each silver particle dispersion of Examples 1 to 5 was diluted 10 times with water, and the spectrum was measured with an ultraviolet / visible spectrometer V-560 manufactured by JASCO Corporation. The results are shown in FIG.
From the results shown in FIG. 2, Examples 1 to 3 having an average aspect ratio larger than 1.5 and containing tabular silver particles of 50% or more are examples in which the main products are spherical silver particles having a small average aspect ratio. Absorption on the long wave side not seen in Examples 4 to 5 was observed.
また、得られた実施例１〜２３及び比較例１〜２の各粒子について、以下のようにして、平均粒子径、平均アスペクト比、粒子形状、及び平板率を測定した。結果を表１−２に示す。 Moreover, about the obtained particle | grains of Examples 1-23 and Comparative Examples 1-2, the average particle diameter, the average aspect ratio, the particle shape, and the flat plate ratio were measured as follows. The results are shown in Table 1-2.
＜平均粒子径、平均アスペクト比、及び粒子形状の測定＞
得られた平板状金属粒子の分散液を、透過型電子顕微鏡観察用のグリッドに載せ、乾燥させた後に、ＴＥＭ（日本電子株式会社製、１２００ＥＸ）観察を行い、粒子形状の判別を行い、撮影したＴＥＭ写真を画像処理することにより各粒子の円相当直径（同一面積の円で表したときの直径）を求め、求めた円相当直径を粒子径ａとした。
また、平板状金属粒子の分散液を、シリコンウェハ上に載せ、乾燥させた後に、原子間力顕微鏡（ＡＦＭ；ＳＩＩ社製、Ｎａｎｏｐｉｃｓ２０００）で平板状金属粒子の厚みを計測し、ＴＥＭ観察より得た粒子径をＡＦＭで得た厚みで割った値の平均値を、平均アスペクト比とした。
<Measurement of average particle diameter, average aspect ratio, and particle shape>
The obtained dispersion of flat metal particles was placed on a grid for observation with a transmission electron microscope and dried, followed by observation with TEM (1200EX manufactured by JEOL Ltd.) to determine the particle shape and photographing. The processed TEM photograph was subjected to image processing to determine the equivalent circle diameter (diameter when represented by a circle of the same area) of each particle, and the obtained equivalent circle diameter was defined as the particle diameter a.
Further, after the dispersion of the flat metal particles is placed on a silicon wafer and dried, the thickness of the flat metal particles is measured with an atomic force microscope (AFM; manufactured by SII, Nanopics 2000), and obtained by TEM observation. The average value obtained by dividing the particle diameter by the thickness obtained by AFM was defined as the average aspect ratio.
＜平板率＞
ＴＥＭ写真で観察された金属粒子を任意に２００個選び出し、平板状金属粒子の数を算出することにより、平板率を求め、下記の基準で評価した。
〔評価基準〕
◎：平板率が５０％以上
○：平板率が３０％以上５０％未満
△：平板率が３０％未満
<Flat plate ratio>
By arbitrarily selecting 200 metal particles observed in the TEM photograph and calculating the number of flat metal particles, the flat plate ratio was determined and evaluated according to the following criteria.
〔Evaluation criteria〕
◎: Flat plate ratio is 50% or more ○: Flat plate ratio is 30% or more and less than 50% △: Flat plate ratio is less than 30%
＊実施例９中、ＰＶＰの質量平均分子量は、１−ビニル−２−ピロリドンの分子量、モル比は１−ビニル−２−ピロリドン／ＡｇＮＯ３を表す。
（実施例２４）
＜近赤外線吸収フィルタの作製＞
−平板状銀粒子分散液の調製−
実施例２で得られた平板状銀粒子（平均アスペクト比（粒子径／厚み）＝４．６）の１質量％分散液１０．０ｇと、ポリビニルアルコール（株式会社クラレ製、クラレ２３５）５質量％水溶液９０．０ｇを攪拌することにより、平板状銀粒子が分散したポリビニルアルコール水溶液を調製した。
(Example 24)
<Preparation of near infrared absorption filter>
-Preparation of tabular silver particle dispersion-
10.0 g of a 1% by weight dispersion of tabular silver particles (average aspect ratio (particle diameter / thickness) = 4.6) obtained in Example 2 and 5 masses of polyvinyl alcohol (manufactured by Kuraray Co., Ltd., Kuraray 235). By stirring 90.0 g of a% aqueous solution, a polyvinyl alcohol aqueous solution in which tabular silver particles were dispersed was prepared.
−フィルタ及び表示装置の作製−
次に、得られた平板状銀粒子分散溶液をガラス基板上に、塗布バーを用いて１ｍ２あたりの銀量が２００ｍｇ±１０ｍｇとになるように塗布し、５０℃にて３０分間乾燥させ、赤外線遮蔽フィルタを作製した。
-Fabrication of filters and display devices-
Next, the obtained plate-like silver particle dispersion solution was coated on a glass substrate using a coating bar so that the silver amount per 1 m 2 was 200 mg ± 10 mg, and dried at 50 ° C. for 30 minutes, An infrared shielding filter was produced.
作製した赤外線遮蔽フィルタを液晶ディスプレイの液晶表示部の上に配置することにより、観察者と表示部との間の光路中に赤外線遮蔽フィルムを挿入し、以下のようにして赤外線遮蔽効果を評価した。 By placing the prepared infrared shielding filter on the liquid crystal display part of the liquid crystal display, an infrared shielding film was inserted into the optical path between the observer and the display part, and the infrared shielding effect was evaluated as follows. .
−評価−
上記のように赤外線遮蔽フィルタを配置する前の液晶ディスプレイからの発光スペクトルを、分光放射輝度計（ＳＲ−３、トプコン株式会社製）により測定した。続いて、赤外線遮蔽フィルタを液晶ディスプレイ（三星電子株式会社製、ＳｙｎｃＭａｓｔｅｒ１７２Ｘ）の液晶表示部の前に配置した時の液晶ディスプレイからの発光スペクトルを、赤外線遮蔽フィルタを介して、前記と同様に測定した。
その結果、７５０ｎｍ付近のスペクトル吸収が認められ、赤外線遮蔽効果が得られると共に、赤外線遮蔽効果も得られた。また、実施例２４の赤外線遮蔽フィルタは、可視光領域での透明性に優れると共に、耐熱性にも優れていた。
-Evaluation-
The emission spectrum from the liquid crystal display before placing the infrared shielding filter as described above was measured with a spectral radiance meter (SR-3, manufactured by Topcon Corporation). Subsequently, the emission spectrum from the liquid crystal display when the infrared shielding filter was placed in front of the liquid crystal display unit of the liquid crystal display (manufactured by Samsung Electronics Co., Ltd., SyncMaster 172X) was measured in the same manner as described above via the infrared shielding filter. .
As a result, spectral absorption near 750 nm was observed, and an infrared shielding effect was obtained, and an infrared shielding effect was also obtained. In addition, the infrared shielding filter of Example 24 was excellent in transparency in the visible light region and excellent in heat resistance.
（実施例２５）
実施例２４において、実施例２で得られた平板状銀粒子（平均アスペクト比（粒子径／粒子厚み）＝４．６）の１質量％分散液の代わりに、実施例４の銀粒子（平板率５％）を用いた以外は、実施例２４と同様にして、赤外線遮蔽フィルタを作製した。
作製した赤外線遮蔽フィルタを用いて、実施例２４と同様にして、赤外線遮蔽効果を評価したところ、４２０ｎｍ付近に主吸収があるため、赤外線遮蔽効果はやや低かった。
(Example 25)
In Example 24, instead of the 1% by mass dispersion of the tabular silver particles (average aspect ratio (particle diameter / particle thickness) = 4.6) obtained in Example 2, the silver particles (tabular plate) of Example 4 were used. An infrared shielding filter was produced in the same manner as in Example 24 except that the rate was 5%.
When the infrared shielding effect was evaluated using the produced infrared shielding filter in the same manner as in Example 24, the infrared shielding effect was slightly low because of the main absorption near 420 nm.
本発明の平板状金属粒子を含有する平板状金属粒子含有組成物は、例えば赤外線吸収材料、光学フィルタ、配線材料、電極材料、触媒、着色剤、インクジェット用インク、カラーフィルタ用色材、フィルタ、化粧料、偽造防止用インク、電磁波遮蔽膜、表面増強蛍光センサ、表面増強ラマン散乱センサ、生体用マーカー、記録材料、ドラッグデリバリー用薬物担体、バイオセンサ、ＤＮＡチップ、検査薬などの種々の用途に用いることができる。
本発明の赤外線吸収材料は、赤外線遮蔽性に優れているので、例えば赤外線遮蔽フィルタとして、プラズマディスプレイ表示装置、ＥＬ表示装置、ＣＲＴ表示装置、液晶表示装置等の表示装置などに好適に用いられる。
The flat metal particle-containing composition containing the flat metal particles of the present invention includes, for example, an infrared absorbing material, an optical filter, a wiring material, an electrode material, a catalyst, a colorant, an inkjet ink, a color material for a color filter, a filter, For various applications such as cosmetics, anti-counterfeiting inks, electromagnetic shielding films, surface-enhanced fluorescent sensors, surface-enhanced Raman scattering sensors, biomarkers, recording materials, drug carriers for drug delivery, biosensors, DNA chips, and test drugs Can be used.
Since the infrared ray absorbing material of the present invention is excellent in infrared ray shielding properties, for example, as an infrared ray shielding filter, it is suitably used for display devices such as plasma display devices, EL display devices, CRT display devices, and liquid crystal display devices.
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