JP2003342496A - Silica-coated gold particulates, manufacturing method therefor and red pigment - Google Patents
Silica-coated gold particulates, manufacturing method therefor and red pigmentInfo
- Publication number
- JP2003342496A JP2003342496A JP2002155268A JP2002155268A JP2003342496A JP 2003342496 A JP2003342496 A JP 2003342496A JP 2002155268 A JP2002155268 A JP 2002155268A JP 2002155268 A JP2002155268 A JP 2002155268A JP 2003342496 A JP2003342496 A JP 2003342496A
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- Prior art keywords
- silica
- fine particles
- gold
- gold fine
- dispersion
- 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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Abstract
Description
【０００１】[0001]
【発明の技術分野】本発明は、シリカで表面を被覆した
金微粒子およびその製造方法、ならびに該微粒子からな
る赤色顔料に関する。TECHNICAL FIELD The present invention relates to fine gold particles whose surfaces are coated with silica, a method for producing the fine gold particles, and a red pigment comprising the fine particles.
【０００２】[0002]
【発明の技術的背景】塗料、化粧品、印刷インキ、液晶
表示素子用カラーフィルター等には、着色またはカラー
表示のために各種顔料が使用されており、このときの赤
色顔料として、ベンガラ、モリブデン赤、などの無機顔
料が一般的に知られている。しかしながら、この種の赤
色顔料は赤色を呈する４００〜８００ｎｍの波長の吸収
領域において、その吸収領域がブロードであり、このた
め鮮明さや透明感に欠けるという欠点を有している。一
方、粒子径が数十ｎｍの金粒子は５５０ｎｍ付近にシャ
ープな吸収ピークを持ち、鮮明で透明感のある顔料とし
て知られている。しかしながら金粒子を顔料として用い
た場合には、顔料が高温に曝されると、凝集したり、凝
集に伴って変色したり、さらには黒色に変色するという
問題、即ち、耐熱性に関する課題が残されている。BACKGROUND OF THE INVENTION Various pigments are used for coloring or color display in paints, cosmetics, printing inks, color filters for liquid crystal display devices, etc., and red pigments at this time are red iron oxide, molybdenum red, etc. Inorganic pigments such as, are generally known. However, this type of red pigment has a drawback in that it has a broad absorption region in the absorption region having a wavelength of 400 to 800 nm which exhibits a red color, and thus lacks in sharpness and transparency. On the other hand, gold particles having a particle size of several tens of nm have a sharp absorption peak near 550 nm, and are known as clear and transparent pigments. However, when gold particles are used as a pigment, when the pigment is exposed to a high temperature, there are problems such as aggregation, discoloration due to aggregation, and discoloration to black, that is, heat resistance. Has been done.
【０００３】[0003]
【発明の目的】本発明は、上記問題点に鑑みてなされた
ものであり、高温に曝されても鮮明さが低下したり変色
することのない赤色顔料として有用なシリカ被覆金微粒
子およびその製造方法、ならびに該微粒子からなる赤色
顔料を提供するものである。SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and silica-coated gold fine particles useful as a red pigment that does not deteriorate in sharpness or discolor even when exposed to high temperatures, and their production. A method and a red pigment comprising the fine particles are provided.
【０００４】[0004]
【発明の概要】本発明に係るシリカ被覆金微粒子は、平
均粒子径（ＤG ）が２ｎｍ〜５０ｎｍの範囲にある金微
粒子の表面をシリカで被覆したことを特徴としている。
前記シリカ被覆金微粒子は、平均粒子径（ＤP ）が４ｎ
ｍ〜１５０ｎｍの範囲にあることが好ましい。本発明に
係るシリカ被覆金微粒子の製造方法は、平均粒子径（Ｄ
G ）が２ｎｍ〜５０ｎｍの範囲にある金微粒子の水分散
液または水と有機溶媒混合分散液に、界面活性剤を添加
し、ついで、アルカリを添加して分散液のｐＨを９〜１
２の範囲に調整し、必要に応じて加熱熟成し、酸性珪酸
液またはシリカゾルを添加することを特徴としている。
本発明に係る赤色顔料は前記シリカ被覆金微粒子からな
ることを特徴としている。Silica-coated gold particles according to the present invention SUMMARY OF THE INVENTION is characterized in that the average particle diameter (D G) is coated with a surface of gold particles in the range of 2nm~50nm silica.
The silica-coated gold fine particles have an average particle diameter (D P ) of 4n.
It is preferably in the range of m to 150 nm. The method for producing silica-coated gold fine particles according to the present invention has an average particle diameter (D
G ) is in the range of 2 nm to 50 nm, a surfactant is added to an aqueous dispersion of fine gold particles or a mixed dispersion of water and an organic solvent, and then an alkali is added to adjust the pH of the dispersion to 9 to 1
It is characterized in that it is adjusted to the range of 2, and if necessary, it is heat-aged and an acidic silicic acid solution or silica sol is added.
The red pigment according to the present invention is characterized by comprising the silica-coated gold fine particles.
【０００５】[0005]
【発明の具体的説明】以下、本発明について具体的に説
明する。DETAILED DESCRIPTION OF THE INVENTION The present invention will be specifically described below.
【０００６】シリカ被覆金粒子
本発明に係るシリカ被覆金微粒子は、平均粒子径
（ＤG ）が２ｎｍ〜５０ｎｍの範囲にある金微粒子の表
面をシリカで被覆したものであり、金微粒子の平均粒子
径は、特に、２〜３０ｎｍの範囲にあることが好まし
い。平均粒子径が２ｎｍ未満の場合は、プラズモン吸収
による光吸収波長が４００ｎｍ未満となり、鮮明で透明
感のある赤色顔料としての金微粒子の鮮明さ、透明感が
低下する。平均粒子径が５０ｎｍを越えると、５５０ｎ
ｍ付近の吸収が低下し、赤色を呈さなくなる。また、分
散性が低下するので、均一にシリカを被覆したり、単分
散の状態のシリカ被覆金粒子を得ることが困難となり、
このため鮮明で透明感のある赤色顔料のためのシリカ被
覆金微粒子を得ることが困難となる。[0006] Silica-coated gold particles according to the silica-coated gold particles present invention has an average particle diameter (D G) is coated with a surface of gold particles in the range of 2nm~50nm silica, average particle gold particles The diameter is particularly preferably in the range of 2 to 30 nm. When the average particle size is less than 2 nm, the light absorption wavelength due to plasmon absorption is less than 400 nm, and the sharpness and transparency of the fine gold particles as a clear and transparent red pigment deteriorate. If the average particle size exceeds 50 nm, 550n
Absorption in the vicinity of m is reduced and the red color is not exhibited. Further, since the dispersibility is reduced, it is difficult to uniformly coat silica or obtain silica-coated gold particles in a monodispersed state,
For this reason, it becomes difficult to obtain fine particles of silica-coated gold for a clear and transparent red pigment.
【０００７】上記金微粒子としては、平均粒子径が上記
範囲にある従来公知の金微粒子を用いることができ、特
に、粒子径分布が揃った金微粒子を用いると吸収領域の
広がりを抑制でき、鮮明で透明感のあるシリカ被覆金微
粒子を得ることができる。本発明に用いる金微粒子は、
例えば、金化合物水溶液に還元剤を加えることによって
製造することができる。また、金化合物水溶液に超音波
を照射することによっても得ることができる。As the gold fine particles, conventionally known gold fine particles having an average particle size in the above range can be used. Particularly, when gold fine particles having a uniform particle size distribution are used, it is possible to suppress the spread of the absorption region, and it is clear. Thus, it is possible to obtain transparent silica-coated gold fine particles. The fine gold particles used in the present invention are
For example, it can be produced by adding a reducing agent to the gold compound aqueous solution. It can also be obtained by irradiating the gold compound aqueous solution with ultrasonic waves.
【０００８】本発明においてシリカ被覆層の厚さは１〜
５０ｎｍ、特に１〜２０ｎｍの範囲にあることが好まし
い。金微粒子がシリカで被覆されていると、製造および
使用時に高温の熱履歴を受けても凝集したり、凝集に伴
って変色することが抑制され、鮮明で透明感を有すると
ともに耐熱性に優れた赤色顔料としてのシリカ被覆金微
粒子が得られる。シリカ被覆層の厚さが１ｎｍ未満の場
合は、凝集を抑制する効果が不充分となり、耐熱性が不
充分となることがある。シリカ被覆層の厚さが５０ｎｍ
を越えると、シリカ被覆層による光の散乱が顕著とな
り、桃色さらには白色を呈するようになる。従って、本
発明に係るシリカ被覆金微粒子は平均粒子径（ＤP ）が
４〜１５０ｎｍ、さらには４〜１００ｎｍの範囲にある
ことが好ましい。In the present invention, the silica coating layer has a thickness of 1 to
It is preferably in the range of 50 nm, particularly 1 to 20 nm. When the fine gold particles are coated with silica, they are prevented from agglomerating even when subjected to a high temperature heat history during production and use, and discoloration due to agglomeration is suppressed, and they have a clear and transparent feeling and are excellent in heat resistance. Silica-coated gold fine particles as a red pigment are obtained. If the thickness of the silica coating layer is less than 1 nm, the effect of suppressing aggregation may be insufficient and the heat resistance may be insufficient. Thickness of silica coating is 50 nm
When it exceeds, the scattering of light by the silica coating layer becomes remarkable, and pink or even white is exhibited. Therefore, the silica-coated gold fine particles according to the present invention preferably have an average particle diameter (D P ) of 4 to 150 nm, more preferably 4 to 100 nm.
【０００９】なお、本発明のシリカ被覆金微粒子におい
て、鮮明で透明感を有するとともに耐熱性に優れた赤色
顔料を得ることができれば、シリカに代えて他の金属酸
化物（例えば、アルミナ、ジルコニア、チタニア等）、
複合金属酸化物（例えば、シリカ・アルミナ、シリカ・
ジルコニア、シリカ・チタニア等）を用いることも可能
である。If a red pigment having a clear and transparent feeling and excellent heat resistance can be obtained from the silica-coated gold fine particles of the present invention, other metal oxides (eg, alumina, zirconia, Titania, etc.),
Complex metal oxides (eg silica-alumina, silica-
It is also possible to use zirconia, silica-titania, etc.).
【００１０】シリカ被覆金微粒子の製造方法
ついで、本発明に係るシリカ被覆金微粒子の製造方法に
ついて説明する。本発明に係るシリカ被覆金微粒子の製
造方法は、平均粒子径（ＤG ）が２ｎｍ〜５０ｎｍの範
囲にある金微粒子の水分散液または水と有機溶媒混合分
散液に、界面活性剤を添加し、ついで、アルカリを添加
して分散液のｐＨを９〜１２の範囲に調整し、必要に応
じて加熱熟成し、酸性珪酸液またはシリカゾルを添加す
ることを特徴としている。金微粒子としては前記した金
微粒子を用いることができる。また、分散媒としては、
水または水と有機溶媒を用いるが、有機溶媒としてはメ
タノール、エタノール、プロパノール、ブタノール、ジ
アセトンアルコール、フルフリルアルコール、テトラヒ
ドロフルフリルアルコール、エチレングリコール、ヘキ
シレングリコールなどのアルコール類；酢酸メチルエス
テル、酢酸エチルエステルなどのエステル類；ジエチル
エーテル、エチレングリコールモノメチルエーテル、エ
チレングリコールモノエチルエーテル、エチレングリコ
ールモノブチルエーテル、ジ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モノエチルエーテ
ルなどのエーテル類；アセトン、メチルエチルケトン、
アセチルアセトン、アセト酢酸エステルなどのケトン
類；ジメチルホルムアミド等のアミド類；などが挙げら
れる。これらは単独で使用してもよく、また２種以上混
合して使用してもよい。この中では特に、メタノール、
エタノール、プロパノール、ブタノール、ジアセトンア
ルコール、フルフリルアルコール、テトラヒドロフルフ
リルアルコール、エチレングリコール、ヘキシレングリ
コールなどのアルコール類が、金微粒子を安定して単分
散させる点で好ましい。この理由は必ずしも明らかでは
ないが、アルコール類と界面活性剤との高い親和性に起
因して、均一なシリカ被覆層が形成されるものと推測さ
れる。 Method for producing silica-coated gold fine particles Next, a method for producing the silica-coated gold fine particles according to the present invention will be described. Method for producing a silica-coated gold particles according to the present invention, the aqueous dispersion or water and an organic solvent mixed dispersion of gold fine particles having a mean particle size of (D G) is in the range of 2 nm to 50 nm, a surfactant is added Then, an alkali is added to adjust the pH of the dispersion to a range of 9 to 12, and the mixture is heat-aged if necessary, and an acidic silicic acid solution or silica sol is added. The gold fine particles described above can be used as the gold fine particles. Further, as the dispersion medium,
Water or water and an organic solvent are used, and as the organic solvent, alcohols such as methanol, ethanol, propanol, butanol, diacetone alcohol, furfuryl alcohol, tetrahydrofurfuryl alcohol, ethylene glycol and hexylene glycol; acetic acid methyl ester, Esters such as acetic acid ethyl ester; ethers such as diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether; acetone, methyl ethyl ketone,
Ketones such as acetylacetone and acetoacetate; amides such as dimethylformamide; and the like. These may be used alone or in combination of two or more. Among these, especially methanol,
Alcohols such as ethanol, propanol, butanol, diacetone alcohol, furfuryl alcohol, tetrahydrofurfuryl alcohol, ethylene glycol and hexylene glycol are preferable from the viewpoint of stably monodispersing the gold fine particles. The reason for this is not clear, but it is presumed that a uniform silica coating layer is formed due to the high affinity between the alcohol and the surfactant.
【００１１】金微粒子分散液中の金微粒子の濃度は０.
１〜５重量％、さらには０. ２〜２重量％の範囲にある
ことが好ましい。金微粒子の濃度が０. １重量％未満の
場合は、シリカ被覆効率（シリカの利用率）が低く、生
産効率も低くなり好ましくない。一方、金微粒子の濃度
が５重量％を越えると分散液の安定性が低下し、酸性珪
酸液またはシリカゾルを添加する際に金微粒子がゲル化
したり、酸性珪酸液またはシリカゾルがゲル化し、均一
なシリカ被覆層を形成することができないことがある。The concentration of the fine gold particles in the fine gold particle dispersion is 0.
It is preferably in the range of 1 to 5% by weight, more preferably 0.2 to 2% by weight. When the concentration of the fine gold particles is less than 0.1% by weight, the silica coating efficiency (silica utilization rate) is low and the production efficiency is low, which is not preferable. On the other hand, if the concentration of the fine gold particles exceeds 5% by weight, the stability of the dispersion is reduced, and the fine gold particles gel when the acidic silicic acid solution or silica sol is added, or the acidic silicic acid solution or silica sol gels, resulting in a uniform It may not be possible to form a silica coating layer.
【００１２】金微粒子分散液に添加する界面活性剤とし
ては、カチオン界面活性剤が好ましい。カチオン界面活
性剤は金微粒子の表面に配位して、表面が正電荷を有す
るようになり、これに負電荷を有する酸性珪酸液やシリ
カゾルが効率的に付着・凝集し、シリカが析出して、シ
リカ被覆層を形成するようになる。カチオン界面活性剤
としては、脂肪族アミン塩およびそのアンモニウム
塩、芳香族４級アンモニウム塩、複素環４級アンモ
ニウム塩等、従来公知のカチオン界面活性剤を用いるこ
とができる。As the surfactant added to the gold fine particle dispersion liquid, a cationic surfactant is preferable. The cationic surfactant is coordinated to the surface of the fine gold particles, and the surface becomes positively charged, and the acidic silicic acid solution or silica sol having a negative charge is efficiently attached and aggregated on the surface of the fine gold particles to deposit silica. , To form a silica coating layer. As the cationic surfactant, a conventionally known cationic surfactant such as an aliphatic amine salt and its ammonium salt, an aromatic quaternary ammonium salt, or a heterocyclic quaternary ammonium salt can be used.
【００１３】界面活性剤の添加量は、最終的に得られる
金微粒子の表面をシリカで充分覆い、耐熱性を向上でき
る程度に用いればよく、用いる金微粒子の平均粒子径に
よっても異なるが、金微粒子水分散液または水と有機溶
媒混合分散液中の濃度が概ね０. ２〜２０重量％、さら
には０. ５〜１０重量％の範囲になるように添加するこ
とが好ましい。界面活性剤の濃度が０. ２重量％未満の
場合は、金微粒子表面に配位する界面活性剤が少ないた
めにシリカが充分析出せず、前記した範囲の厚みを有す
る被覆層が形成され難い。界面活性剤の濃度が２０重量
％を越えても、金微粒子表面の界面活性剤が増えること
も、正電荷が増すこともなく、逆に、シリカの析出を阻
害したり、経済性が低下することがある。The amount of the surfactant added may be such that the surface of the finally obtained gold fine particles is sufficiently covered with silica and the heat resistance can be improved. It depends on the average particle size of the gold fine particles to be used. It is preferable to add the fine particle water dispersion or the water / organic solvent mixture dispersion so that the concentration thereof is in the range of about 0.2 to 20% by weight, and more preferably 0.5 to 10% by weight. If the concentration of the surfactant is less than 0.2% by weight, the amount of the surfactant coordinated to the surface of the fine gold particles is small, so that silica is not sufficiently deposited, and it is difficult to form a coating layer having a thickness within the above range. . Even when the concentration of the surfactant exceeds 20% by weight, the amount of the surfactant on the surface of the gold fine particles does not increase and the positive charge does not increase, and on the contrary, the precipitation of silica is hindered and the economical efficiency is reduced. Sometimes.
【００１４】なお、別の方法として、金としての濃度が
０. １〜５重量％の範囲にある金化合物水溶液または水
／有機溶媒混合溶媒溶液に、前記同様の界面活性剤を添
加し、ついで還元剤を添加することによって上記と同様
の界面活性剤を添加した金微粒子分散液を得ることがで
きる。このときの還元剤としては、金化合物の金を還元
して金微粒子を得ることができれば特別の制限はなく、
硫酸第一鉄、クエン酸三ナトリウム、酒石酸、水素化ホ
ウ素ナトリウム、次亜リン酸ナトリウムなどが挙げられ
る。また、有機溶媒としては前記同様のものを用いるこ
とができ、この場合もアルコール溶媒を用いることが好
ましい。As another method, a surfactant similar to the above is added to a gold compound aqueous solution or a water / organic solvent mixed solvent solution having a gold concentration of 0.1 to 5% by weight, and then added. By adding a reducing agent, a gold fine particle dispersion liquid containing the same surfactant as described above can be obtained. The reducing agent at this time is not particularly limited as long as gold of the gold compound can be reduced to obtain fine gold particles,
Examples thereof include ferrous sulfate, trisodium citrate, tartaric acid, sodium borohydride, sodium hypophosphite and the like. As the organic solvent, the same ones as described above can be used, and in this case also, it is preferable to use the alcohol solvent.
【００１５】ついで、界面活性剤を添加した金微粒子分
散液にアルカリを添加して分散液のｐＨを９〜１２、好
ましくは９〜１１の範囲に調整する。アルカリとしては
ＮａＯＨ、ＫＯＨ、ＲｂＯＨ、ＣｓＯＨ等を用いること
ができ、これらアルカリ金属の水溶液を添加することに
よってｐＨ調整を行う。金微粒子分散液のｐＨが９未満
の場合は、シリカの溶解度が低いために金微粒子表面に
シリカが析出せず、シリカ微粒子が生成したり、シリカ
ゾルがゲル化して、シリカ被覆金微粒子が得られないこ
とがある。金微粒子分散液のｐＨが１２を越えると、シ
リカの溶解度が高いために金微粒子表面へのシリカの析
出が抑制されたり、シリカゾルの付着速度が低下した
り、析出しないことがある。Then, an alkali is added to the gold fine particle dispersion containing a surfactant to adjust the pH of the dispersion to 9 to 12, preferably 9 to 11. As the alkali, NaOH, KOH, RbOH, CsOH or the like can be used, and the pH is adjusted by adding an aqueous solution of these alkali metals. When the pH of the gold fine particle dispersion liquid is less than 9, silica is not deposited on the surface of the gold fine particles due to the low solubility of silica, silica fine particles are generated, or silica sol is gelated to obtain silica-coated gold fine particles. Sometimes there is not. When the pH of the gold fine particle dispersion exceeds 12, the solubility of silica is high, so that the precipitation of silica on the surface of the gold fine particles may be suppressed, or the deposition rate of silica sol may be reduced or may not occur.
【００１６】ついで、上記ｐＨを調整した金微粒子分散
液に酸性珪酸液またはシリカゾルを添加する。酸性珪酸
液としては、例えば、珪酸ソーダ、珪酸カリウム等のア
ルカリ金属珪酸塩の水溶液をイオン交換樹脂等で脱アル
カリして得られる酸性珪酸液が好ましい。また、シリカ
ゾルとしては従来公知のシリカゾルを用いることがで
き、例えば、本願出願人の出願による特開昭６３−４５
１１４号公報、特開昭６３−６４９１１号公報に開示し
たシリカゾルはシリカ粒子径が均一であり、安定性に優
れているので好ましい。Next, an acidic silicic acid solution or silica sol is added to the gold fine particle dispersion liquid whose pH has been adjusted. The acidic silicic acid solution is preferably an acidic silicic acid solution obtained by dealkalizing an aqueous solution of an alkali metal silicate such as sodium silicate or potassium silicate with an ion exchange resin or the like. Further, as the silica sol, a conventionally known silica sol can be used. For example, JP-A-63-45 filed by the applicant of the present application can be used.
The silica sol disclosed in Japanese Patent Application Laid-Open No. 114 and Japanese Patent Application Laid-Open No. 63-64911 is preferable because it has a uniform silica particle diameter and is excellent in stability.
【００１７】酸性珪酸液を用いる場合、酸性珪酸液の添
加量は、金微粒子の平均粒子径によっても異なるが、金
微粒子１重量部当たりＳｉＯ2 として０. ０１〜２０重
量部、さらには０. ０２〜５重量部の範囲にあることが
好ましい。酸性珪酸液の添加量が０. ０１重量部未満の
場合は、前記した範囲の厚みを有するシリカ被覆層を形
成できず、耐熱性が不充分となることがある。酸性珪酸
液の添加量が２０重量部を越えてもさらに耐熱性が向上
することもなく、また、シリカ被覆層の厚さが厚くなり
過ぎて光の散乱の原因となり、桃色さらには白色を呈す
るようになることがある。また、酸性珪酸液の添加速度
は、前記耐熱性を発現できるシリカ被覆層を形成できれ
ば特に制限はなく、シリカ被覆層の形成に与らないシリ
カ微粒子が生成しない範囲で時間を掛けて添加すること
が好ましい。When an acidic silicic acid solution is used, the amount of the acidic silicic acid solution added varies depending on the average particle size of the gold fine particles, but 0.01 to 20 parts by weight, and more preferably 0.02 parts by weight as SiO 2 per 1 part by weight of the gold fine particles. It is preferably in the range of 02 to 5 parts by weight. If the amount of the acidic silicic acid solution added is less than 0.01 part by weight, a silica coating layer having a thickness within the above range cannot be formed and heat resistance may be insufficient. Even if the amount of the acidic silicic acid solution added exceeds 20 parts by weight, the heat resistance does not further improve, and the silica coating layer becomes too thick, causing light scattering, giving a pink or even white color. It may happen. The addition rate of the acidic silicic acid solution is not particularly limited as long as a silica coating layer capable of exhibiting the heat resistance can be formed, and the addition should be carried out over a period of time within the range where silica fine particles that do not contribute to the formation of the silica coating layer are not formed. Is preferred.
【００１８】次に、シリカゾルを用いる場合、シリカゾ
ルの添加量は、金微粒子の平均粒子径によっても異なる
が、金微粒子１重量部当たりＳｉＯ2 として０. １〜２
０重量部、さらには１〜１０重量部の範囲にあることが
好ましい。シリカゾルの添加量が０. １重量部未満の場
合は、耐熱性が不充分となることがある。シリカゾルの
添加量が２０重量部を越えてもさらに耐熱性が向上する
こともなく、また、シリカ被覆層の厚さが厚くなり過ぎ
て光の散乱の原因となり、桃色さらには白色を呈するよ
うになることがある。また、シリカゾルの添加速度は、
前記耐熱性を発現できるシリカ被覆層を形成できれば特
に制限はなく、シリカ被覆量が少ない場合は一時に添加
することも可能である。Next, when silica sol is used, the addition amount of silica sol varies depending on the average particle diameter of gold fine particles, but 0.1 to 2 as SiO 2 per 1 part by weight of gold fine particles.
It is preferably 0 part by weight, more preferably 1 to 10 parts by weight. When the amount of silica sol added is less than 0.1 part by weight, heat resistance may be insufficient. Even if the amount of silica sol added exceeds 20 parts by weight, the heat resistance does not further improve, and the thickness of the silica coating layer becomes too thick, which causes light scattering, resulting in a pink or white color. May be. The addition rate of silica sol is
There is no particular limitation as long as the silica coating layer capable of exhibiting the heat resistance can be formed, and when the silica coating amount is small, it can be added at a time.
【００１９】前記シリカゾル中のシリカ粒子の平均粒子
径は４〜５０ｎｍ、さらには５〜３０ｎｍの範囲にある
ことが好ましい。シリカ粒子の平均粒子径が４ｎｍ未満
のものは、安定なシリカゾルとして得ることが困難であ
り、他方、平均粒子径が５０ｎｍを越えると、金微粒子
表面に付着・析出することが困難であり、また被覆でき
たとしてもシリカ被覆層が厚くなり過ぎて光の散乱の原
因となり、桃色さらには白色を呈するようになることが
ある。本発明の製造方法では、前記酸性珪酸液またはシ
リカゾルを添加した後、必要に応じて熟成することがで
きる。具体的には、３０〜１５０℃、好ましくは５０〜
１００℃で、数時間加熱処理すれば良く、このような加
熱熟成を行うことにより、一層緻密なシリカ被覆層を形
成したり、一層均一な厚みのシリカ被覆層を形成するこ
とができる。The average particle size of the silica particles in the silica sol is preferably 4 to 50 nm, more preferably 5 to 30 nm. If the average particle size of the silica particles is less than 4 nm, it is difficult to obtain a stable silica sol. On the other hand, if the average particle size exceeds 50 nm, it is difficult to deposit / precipitate on the surface of the gold fine particles. Even if it can be coated, the silica coating layer becomes too thick and causes light scattering, which may cause pink or even white. In the production method of the present invention, the acidic silicic acid solution or silica sol may be added and then aged if necessary. Specifically, 30 to 150 ° C., preferably 50 to
It suffices to perform heat treatment at 100 ° C. for several hours, and by performing such heat aging, a more dense silica coating layer or a silica coating layer having a more uniform thickness can be formed.
【００２０】赤色顔料
本発明に係る赤色顔料は前記シリカ被覆金微粒子からな
っている。前記シリカ被覆金微粒子は金微粒子の平均粒
子径が２〜５０ｎｍの範囲にあるので、波長４８０〜６
００ｎｍの狭い範囲に吸収ピークをもち、このため鮮明
で透明感のある赤色顔料として有用である。さらに金微
粒子はシリカで被覆されているので、例えば、５００℃
以上の高温に曝されても凝集したり、凝集に伴って変色
することがなく、鮮明で透明感のある赤色を維持するこ
とができ、耐熱性に優れた赤色顔料として有用である。 Red Pigment The red pigment according to the present invention comprises the silica-coated gold fine particles. The silica-coated gold fine particles have a wavelength of 480 to 6 because the average particle size of the gold fine particles is in the range of 2 to 50 nm.
Since it has an absorption peak in a narrow range of 00 nm, it is useful as a clear and transparent red pigment. Furthermore, since the fine gold particles are coated with silica, for example, 500 ° C
It is useful as a red pigment excellent in heat resistance since it can maintain a clear and transparent red color without agglomeration or discoloration due to the agglomeration even when exposed to the above high temperature.
【００２１】[0021]
【発明の効果】本発明に係るシリカ被覆金微粒子は、金
微粒子の平均粒子径が特定範囲にあるので鮮明で透明感
のある赤色を呈すると共に、金微粒子がシリカで被覆さ
れているので高温に曝されても金微粒子が凝集したり粒
子成長することがない。このため、鮮明さや透明感を低
下させたり変色することがなく、耐熱性に優れた赤色顔
料を得ることができる。本発明に係るシリカ被覆金微粒
子の製造方法によれば、前記シリカ被覆金微粒子を簡易
かつ効率的に製造することができる。本発明に係る赤色
顔料は耐熱性に優れ、塗料、化粧品、印刷インキ、液晶
表示素子用カラーフィルター等に用いる顔料として有用
である。EFFECTS OF THE INVENTION The silica-coated gold fine particles according to the present invention show a clear and transparent red color because the average particle size of the gold fine particles is in a specific range, and the gold fine particles are coated with silica, so that they are exposed to high temperatures. Even when exposed, the fine gold particles do not aggregate or grow. For this reason, it is possible to obtain a red pigment having excellent heat resistance without deteriorating the clarity and transparency or discoloring. According to the method for producing silica-coated gold fine particles according to the present invention, the silica-coated gold fine particles can be easily and efficiently produced. The red pigment according to the present invention has excellent heat resistance and is useful as a pigment used in paints, cosmetics, printing inks, color filters for liquid crystal display devices and the like.
【００２２】[0022]
【実施例】以下に本発明の好適な実施例を挙げるが、本
発明はこれら実施例に限定されるものではない。EXAMPLES Preferred examples of the present invention will be given below, but the present invention is not limited to these examples.
【００２３】[0023]
【実施例１】シリカ被覆金微粒子（Ａ）の調製
蒸留水１４１０ｇに塩化金酸４水塩（ＨＡｕＣｌ・４Ｈ
2 Ｏ）１４. ２５ｇを溶解させ、これに界面活性剤（花
王（株）製：コータミン２４Ｐ；ＣＨ3 （ＣＨ 2 ）11Ｎ
（ＣＨ3 ）3 Ｃｌ）２８. ５ｇを添加した。ついで、還
元剤として濃度１重量％の水素化ホウ素ナトリウム（Ｎ
ａＢＨ4 ）７. ７ｇを添加して金微粒子表面にカチオン
界面活性剤が配位した（吸着した）金微粒子分散液を調
製した。このときの金微粒子の平均粒子径を測定し結果
を表１に示した。次に、金微粒子分散液１００ｇを採取
し、これに濃度１重量％のＮａＯＨ水溶液を添加して分
散液のｐＨを１０. ５に調整し、９５℃に昇温し３０分
間加熱した。その後、ＳｉＯ2 濃度３重量％の酸性珪酸
液１. ３ｇを１５分間で添加して、シリカ被覆金微粒子
（Ａ）分散液を調製した。ついで、粒子を分離した後、
１２０℃で１時間乾燥してシリカ被覆金微粒子（Ａ）を
調製した。[Example 1]Preparation of silica-coated gold fine particles (A)
Chloroauric acid tetrahydrate (HAuCl.4H) in 1410 g of distilled water
2O) 14.25 g was dissolved and a surfactant (flower
Ou Co., Ltd .: Coatamine 24P; CH3(CH 2)11N
(CH3)3Cl) 28.5 g was added. Then return
Sodium borohydride with a concentration of 1 wt% (N
aBHFour) Addition of 7.7 g of cations on the surface of the fine gold particles
Prepare a gold fine particle dispersion with a surfactant coordinated (adsorbed)
Made The average particle size of the gold particles at this time was measured and the result
Is shown in Table 1. Next, collect 100 g of gold fine particle dispersion
Then, add 1% by weight NaOH aqueous solution to
Adjust the pH of the dispersion to 10.5 and raise to 95 ° C for 30 minutes.
Heated for a while. After that, SiO2Acidic silica with a concentration of 3% by weight
Liquid 1.3g was added over 15 minutes to obtain silica-coated gold fine particles.
(A) A dispersion was prepared. Then, after separating the particles,
The silica-coated gold fine particles (A) are dried at 120 ° C. for 1 hour.
Prepared.
【００２４】シリカ被覆金微粒子の評価
（１）赤色度（赤色色調の鮮明さ）
シリカ被覆金微粒子（Ａ）について、目視観察により赤
色度を観察し、以下の基準で評価し、結果を表１に示し
た。
鮮明な赤色、透明性あり ：◎
赤色、透明性やや低下 ：○
ピンク色・ピンク色に近い、透明性低下 ：△
白っぽさを増したピンク・白色、透明性無し：×
（２）反射率（赤色度および透明性）
シリカ被覆金微粒子（Ａ）を金の濃度が０．００５重量
％となるように純水に分散させ、反射率を分光光度計
（大塚電子（株）製：MCPD-2000 ）を用いて測定し、波
長４８０〜６００ｎｍの範囲における反射率の平均値と
して表示した。結果を表１に示した。
（３）耐熱性
シリカ被覆金微粒子（Ａ）を７００℃で１時間焼成し、
目視観察によ赤色度を観察し、以下の基準で評価し、結
果を表１に示した。
鮮明な赤色、透明性あり ：◎
赤色、透明性やや低下 ：○
ピンク色・ピンク色に近い、透明性低下 ：△
黒色または金色 ：×
（４）粒子分散性
シリカ被覆金微粒子（Ａ）分散液を１時間静置し、微粒
子の沈降の有無を観察し、以下の基準で評価し、結果を
表１に示した。
微粒子の沈降が認められない：○
微粒子の沈降が認められる ：× Evaluation of Silica-Coated Gold Fine Particles (1) Redness (Clearness of Red Color Tone) The silica-coated gold fine particles (A) were visually observed for redness and evaluated according to the following criteria. It was shown to. Vivid red, with transparency: ◎ Red, with a slight decrease in transparency: ○ Pink / close to pink, decreased transparency: △ Pink / white with increased whiteness, no transparency: × (2) Reflection Ratio (redness and transparency) The silica-coated gold fine particles (A) are dispersed in pure water so that the gold concentration is 0.005% by weight, and the reflectance is measured with a spectrophotometer (Otsuka Electronics Co., Ltd .: MCPD). -2000) and displayed as the average value of the reflectance in the wavelength range of 480 to 600 nm. The results are shown in Table 1. (3) The heat-resistant silica-coated gold fine particles (A) are fired at 700 ° C. for 1 hour,
The degree of redness was visually observed and evaluated according to the following criteria. The results are shown in Table 1. Vivid red, with transparency: ◎ Red, with a slight decrease in transparency: ○ Pink / close to pink, decrease in transparency: △ Black or gold: × (4) Particle-dispersible silica-coated gold fine particles (A) dispersion Was allowed to stand for 1 hour, the presence or absence of sedimentation of fine particles was observed, and the results were shown in Table 1 according to the following criteria. No settling of fine particles: ○ Fine particle settling is observed: ×
【００２５】[0025]
【実施例２】シリカ被覆金微粒子（Ｂ）の調製
実施例１において、ＳｉＯ2 濃度３重量％の酸性珪酸液
３ｇを３０分間で添加した以外は実施例１と同様にし
て、シリカ被覆金微粒子（Ｂ）分散液およびシリカ被覆
金微粒子（Ｂ）を調製した。得られたシリカ被覆金微粒
子（Ｂ）について赤色度、反射率、耐熱性および分散性
を評価し、結果を表１に示した。Example 2 Preparation of silica-coated gold fine particles (B) Silica-coated gold fine particles were prepared in the same manner as in Example 1 except that 3 g of an acidic silicic acid solution having a SiO 2 concentration of 3% by weight was added for 30 minutes. (B) Dispersion and silica-coated gold fine particles (B) were prepared. The obtained silica-coated gold fine particles (B) were evaluated for redness, reflectance, heat resistance and dispersibility, and the results are shown in Table 1.
【００２６】[0026]
【実施例３】シリカ被覆金微粒子（Ｃ）の調製
実施例１において、ＳｉＯ2 濃度３重量％の酸性珪酸液
２４ｇを３０分間で添加した以外は実施例１と同様にし
て、シリカ被覆金微粒子（Ｃ）分散液およびシリカ被覆
金微粒子（Ｃ）を調製した。得られたシリカ被覆金微粒
子（Ｃ）について赤色度、反射率、耐熱性および分散性
を評価し、結果を表１に示した。Example 3 Preparation of silica-coated gold fine particles (C) Silica-coated gold fine particles were prepared in the same manner as in Example 1 except that 24 g of an acidic silicic acid solution having a SiO 2 concentration of 3% by weight was added for 30 minutes. (C) A dispersion and silica-coated gold fine particles (C) were prepared. The obtained silica-coated gold fine particles (C) were evaluated for redness, reflectance, heat resistance and dispersibility, and the results are shown in Table 1.
【００２７】[0027]
【実施例４】シリカ被覆金微粒子（Ｄ）の調製
実施例１において、酸性珪酸液の代わりにシリカゾル
（触媒化成工業（株）製：ＳＩ−５５０、平均粒子径５
ｎｍ、ＳｉＯ2 濃度４８重量％）３. ０ｇを一時に添加
した以外は実施例１と同様にして、シリカ被覆金微粒子
（Ｄ）を調製した。シリカ被覆金微粒子（Ｄ）について
赤色度、反射率、耐熱性および分散性を評価し、結果を
表１に示した。但し、シリカ被覆金微粒子（Ｄ）は沈降
し易く、反射率の測定ができなかった。[Example 4] Preparation of silica-coated gold fine particles (D) In Example 1, instead of the acidic silicic acid solution, silica sol (manufactured by Catalysts & Chemicals Industry Co., Ltd .: SI-550, average particle size 5) was used.
Silica-coated gold fine particles (D) were prepared in the same manner as in Example 1 except that 3.0 g of SiO 2 and 48 wt% of SiO 2 concentration was added at one time. The silica coated gold fine particles (D) were evaluated for redness, reflectance, heat resistance and dispersibility, and the results are shown in Table 1. However, the silica-coated gold fine particles (D) were likely to settle, and the reflectance could not be measured.
【００２８】[0028]
【実施例５】シリカ被覆金微粒子（Ｅ）の調製
実施例４において、シリカゾル（触媒化成工業（株）
製：ＳＩ−５５０、平均粒子径５ｎｍ、ＳｉＯ2 濃度４
８重量％）５. ５ｇを一時に添加した以外は実施例１と
同様にして、シリカ被覆金微粒子（Ｅ）を調製した。シ
リカ被覆金微粒子（Ｅ）について赤色度、反射率、耐熱
性および分散性を評価し、結果を表１に示した。但し、
シリカ被覆金微粒子（Ｅ）は沈降し易く、反射率の測定
ができなかった。Example 5 Preparation of Silica-Coated Gold Fine Particles (E) In Example 4, silica sol (Catalyst Chemical Co., Ltd.)
Made: SI-550, average particle size 5 nm, SiO 2 concentration 4
Silica-coated gold fine particles (E) were prepared in the same manner as in Example 1 except that 5.5 g (8% by weight) was added at one time. The silica coated gold fine particles (E) were evaluated for redness, reflectance, heat resistance and dispersibility, and the results are shown in Table 1. However,
The silica-coated gold fine particles (E) were prone to sedimentation, and the reflectance could not be measured.
【００２９】[0029]
【実施例６】シリカ被覆金微粒子（Ｆ）の調製
実施例４において、シリカゾル（触媒化成工業（株）
製：ＳＩ−５５０、平均粒子径５ｎｍ、ＳｉＯ2 濃度４
８重量％）９. ９ｇを一時に添加した以外は実施例１と
同様にして、シリカ被覆金微粒子（Ｆ）を調製した。シ
リカ被覆金微粒子（Ｆ）について赤色度、反射率、耐熱
性および分散性を評価し、結果を表１に示した。但し、
シリカ被覆金微粒子（Ｆ）は沈降し易く、反射率の測定
ができなかった。Example 6 Preparation of Silica Coated Gold Fine Particles (F) In Example 4, silica sol (Catalyst Chemical Co., Ltd.)
Made: SI-550, average particle size 5 nm, SiO 2 concentration 4
Silica-coated gold fine particles (F) were prepared in the same manner as in Example 1 except that 9.9 g (8% by weight) was added at one time. The silica coated gold fine particles (F) were evaluated for redness, reflectance, heat resistance and dispersibility, and the results are shown in Table 1. However,
The silica-coated gold fine particles (F) were prone to sedimentation, and the reflectance could not be measured.
【００３０】[0030]
【実施例７】シリカ被覆金微粒子（Ｇ）の調製
実施例２において、蒸留水を２８２０ｇ用いた以外は実
施例２と同様にして、金微粒子表面にカチオン界面活性
剤が配位した（吸着した）金微粒子分散液を調製した。
このときの金微粒子の平均粒子径を測定し、結果を表１
に示した。ついで、実施例１と同様にしてシリカ被覆金
微粒子（Ｇ）分散液およびシリカ被覆金微粒子（Ｇ）を
調製した。シリカ被覆金微粒子（Ｇ）について赤色度、
反射率、耐熱性および分散性を評価し、結果を表１に示
した。[Example 7] Preparation of silica-coated gold fine particles (G) In the same manner as in Example 2 except that 2820 g of distilled water was used in Example 2, a cationic surfactant was coordinated (adsorbed) on the surface of the gold fine particles. ) A fine gold particle dispersion was prepared.
The average particle size of the fine gold particles at this time was measured, and the results are shown in Table 1.
It was shown to. Then, a silica-coated gold fine particle (G) dispersion and a silica-coated gold fine particle (G) were prepared in the same manner as in Example 1. Redness of silica-coated gold fine particles (G),
The reflectance, heat resistance and dispersibility were evaluated, and the results are shown in Table 1.
【００３１】[0031]
【比較例１】金微粒子（Ｈ）の調製
実施例１と同様にしてカチオン界面活性剤が配位した
（吸着した）金微粒子分散液を調製した。ついで、この
分散液を１２０℃で乾燥して、金微粒子（Ｈ）を調製し
た。金微粒子（Ｈ）について平均粒子径の測定値と赤色
度、反射率、耐熱性および分散性の評価を表１に示し
た。なお、金微粒子（Ｈ）分散液の色調は鮮明で、透明
感のある赤色であった。Comparative Example 1 Preparation of Gold Fine Particles (H) In the same manner as in Example 1, a gold fine particle dispersion liquid in which a cationic surfactant was coordinated (adsorbed) was prepared. Then, this dispersion was dried at 120 ° C. to prepare gold fine particles (H). Table 1 shows the measured values of the average particle size and the evaluation of redness, reflectance, heat resistance and dispersibility of the gold fine particles (H). The color tone of the gold fine particle (H) dispersion was clear and red with a transparent feeling.
【００３２】[0032]
【比較例２】金微粒子（Ｉ）の調製
実施例７と同様にしてカチオン界面活性剤が配位した
（吸着した）金微粒子分散液を調製した。ついで１２０
℃で乾燥して、金微粒子（Ｉ）を調製した。金微粒子
（Ｉ）について平均粒子径の測定値と赤色度、反射率、
耐熱性および分散性の評価を表１に示した。なお、金微
粒子（Ｉ）分散液の色調は鮮明で、透明感のある赤色で
あった。Comparative Example 2 Preparation of Gold Fine Particles (I) In the same manner as in Example 7, a gold fine particle dispersion liquid in which a cationic surfactant was coordinated (adsorbed) was prepared. Then 120
By drying at 0 ° C., gold fine particles (I) were prepared. For the gold fine particles (I), measured values of average particle size, redness, reflectance,
The evaluation of heat resistance and dispersibility is shown in Table 1. In addition, the color tone of the gold fine particle (I) dispersion liquid was clear and was a transparent red color.
【００３３】[0033]
【表１】 金微粒子 シリカ被覆金微粒子 金微粒子の評価 の粒子径 被覆層 重量比 粒径 赤色 反射 耐熱 分散 Ｄ G 種類 厚さ (SiO 2 /Au) Ｄ P 度 率 性 性 (nm) (*1) (nm) (nm) (%) 実施例１ 15 Ｌ 2.6 0.08 20 ◎ 0.5 ◎ ○ 実施例２ 15 Ｌ 5 0.19 25 ◎ 0.5 ◎ ○ 実施例３ 15 Ｌ 20 1.5 55 ○ 0.8 ○ ○ 実施例４ 15 Ｓ 28 3.0 71 ○ − ○ × 実施例５ 15 Ｓ 37 5.0 89 ○ − ○ × 実施例６ 15 Ｓ 48 10 111 ○ − ○ × 実施例７ 5 Ｌ 1.5 0.19 8 ◎ 0.5 ○ ○ ・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・ 比較例１ 15 − − 0 − × 0.5 × ○ 比較例２ 5 − − 0 − × 0.5 × ○ (*1) Ｌ：酸性珪酸液、Ｓ：シリカゾルTABLE 1 Gold fine particulate silica coated gold particle size coating layer weight ratio The particle size of the evaluation of fine gold particles reflected red heat dispersion D G type thickness (SiO 2 / Au) D P of rate of resistance (nm) (* 1 ) (nm) (nm) (%) Example 1 15 L 2.6 0.08 20 ◎ 0.5 ◎ ○ Example 2 15 L 5 0.19 25 ◎ 0.5 ◎ ○ Example 3 15 L 20 1.5 55 ○ 0.8 ○ ○ Example 4 15 S 28 3.0 71 ○ − ○ × Example 5 15 S 37 5.0 89 ○ − ○ × Example 6 15 S 48 10 111 ○ − ○ × Example 7 5 L 1.5 0.19 8 ◎ 0.5 ○ ○ Comparative Example 1 15 − − 0 − × 0.5 × ○ Comparative Example 2 5 − − 0 − × 0.5 × ○ (* 1) L: Acidic silicic acid solution, S: Silica sol
───────────────────────────────────────────────────── フロントページの続き Ｆターム(参考） 4C083 AB191 AB192 BB23 BB25 CC11 DD17 EE01 EE03 4J037 AA04 CA24 EE03 FF03 FF06 ─────────────────────────────────────────────────── ─── Continued front page F-term (reference) 4C083 AB191 AB192 BB23 BB25 CC11 DD17 EE01 EE03 4J037 AA04 CA24 EE03 FF03 FF06
Claims (4)
の範囲にある金微粒子の表面をシリカで被覆したことを
特徴とするシリカ被覆金微粒子。1. An average particle diameter (D G ) of 2 nm to 50 nm
The silica-coated gold fine particles are characterized in that the surfaces of the gold fine particles in the range are covered with silica.
ｍの範囲にある請求項１記載のシリカ被覆金微粒子。2. The average particle diameter (D P ) is 4 nm to 150 n.
The silica-coated gold fine particles according to claim 1, which are in the range of m.
の範囲にある金微粒子の水分散液または水と有機溶媒混
合分散液に、界面活性剤添加し、ついで、アルカリを添
加して分散液のｐＨを９〜１２の範囲に調整し、必要に
応じて加熱熟成し、酸性珪酸液またはシリカゾルを添加
することを特徴とする請求項１または請求項２記載のシ
リカ被覆金微粒子の製造方法。3. The average particle diameter (D G ) is 2 nm to 50 nm.
To the aqueous dispersion of fine gold particles or the mixed dispersion of water and an organic solvent in the range of, a surfactant is added, and then an alkali is added to adjust the pH of the dispersion to the range of 9 to 12, and if necessary, A method for producing silica-coated gold fine particles according to claim 1 or 2, characterized in that the acidic silicic acid solution or silica sol is added after aging by heating.
覆金微粒子からなる赤色顔料。4. A red pigment comprising the silica-coated gold fine particles according to claim 1.
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