JP5691136B2 - Method for producing particle dispersion and method for producing oxide semiconductor particles, metal particles, and metalloid particles - Google Patents

Description

The present invention relates to a method of producing a method of the oxide semiconductor particles to produce a particle dispersion obtained by dispersing oxide semiconductor particles and drying the produced particle dispersion in this method, the metal particles and metalloid particles It is.

  Conventionally, a method for producing metal nanoparticles by dissolving a compound having a 1,4-glucoside bond and a metal compound in a solvent and reducing metal ions in the resulting solution to form metal nanoparticles (for example, Patent Document 1) Reference). In this method for producing metal nanoparticles, the metal ions are reduced by heating the solution and then adding a reducing agent. Thus, monodispersed and fine metal nanoparticles can be produced by a very simple method.

JP 2003-213111 A (claims 1 and 4, paragraph [0032])

However, in the method for producing metal nanoparticles shown in the above-mentioned conventional Patent Document 1, since the reduction reaction relies on the self-decomposition of the organic metal, the reaction tends to occur non-uniformly and aggregates are easily generated. There was a problem that it was difficult to obtain and the yield was poor.
An object of the present invention is to provide a method for producing a particle dispersion , oxide semiconductor particles, and metal particles, which can impart or improve conductivity, dispersibility, dispersion stability, transparency, anti-settling property, etc. very simply. And it is providing the manufacturing method of metalloid particle | grains .

As shown in FIG. 1, the first aspect of the present invention is that an inert gas atmosphere is added to one or two or more single substances or mixtures selected from the group consisting of organic metal compounds and organic metalloid compounds . Colloidal particle dispersion that maintains the ink state peculiar to colloid without being dispersed for more than 2 weeks by irradiating microwaves with an output of 800 to 1250 W for 3 to 10 minutes in a reducing gas atmosphere or air atmosphere A method for producing a particle dispersion including a step of producing a body.
In the method for producing the particle dispersion according to the first aspect, when the single substance or mixture is irradiated with microwaves in a predetermined atmosphere, the molecules of the single substance or mixture are vibrated by the microwaves, and frictional heat is generated. Since it is heated by being generated, the metal or metal oxide in the organometallic compound or the metalloid or metalloid oxide in the organic metalloid compound is mainly centered on the metalorganic compound or organic metalloid while chemically reacting. Decomposes metal compounds. The decomposition of the organometallic compound or the organometalloid compound causes the dissociated organic substance or its decomposition product to be similarly attached to the surface of the particles made of the unbonded metal, semimetal or oxide product thereof. Thus, a particle dispersion used as a film having properties such as conductivity, dispersibility, dispersion stability, transparency, and anti-settling property can be obtained.

In the method for producing a particle dispersion of the first aspect, the one or more single compounds or mixtures selected from the group consisting of organic metal compound and an organic metalloid compound, in a predetermined atmosphere hoax Micro by morphism wave irradiation, so to prepare a colloidal particle dispersion to maintain the colloidal specific ink state without precipitation particles dispersed least 2 weeks, quite conveniently, conductivity, dispersibility, dispersion stability A particle dispersion having improved or improved properties, transparency, anti-settling property, etc. can be obtained.

It is a section lineblock diagram of an apparatus which manufactures a particle dispersion of an embodiment of the present invention experimentally. It is a perspective view of a stainless steel photomask.

Next, an embodiment for carrying out the present invention will be described with reference to the drawings.
<First Embodiment>
As shown in FIG. 1, in order to produce a particle dispersion, first, one or two or more single substances selected from the group consisting of an organic metal compound and an organic metalloid compound are prepared or a mixture is prepared. To do. The metal contained in the organometallic compound is Cu, Au, Ag, Pt, Pd, Ru, Rh, Re, Os, Ir, Sc, Y, Ti, Zr, V, Nb, Ta, Cr, Mo, W, Selected from the group consisting of Mn, Fe, Co, Ni, Zn, Cd, Al, Ga, In, Tl, Sn, Pb, La, Ce, Nd, Sm, Eu, Gd, Tb, Er, Tm and Yb One or more metals, preferably one selected from the group consisting of Cu, Au, Ag, Pt, Pd, Ru, Rh, Re, Ti, Fe, Co, Ni, Zn, In and Sn Two or more metals. The metalloid contained in the organic metalloid compound is one or more metalloids selected from the group consisting of Si, Ge, Sb and Bi.

  The organic component of the organic metal compound or organic metalloid compound is one or more compounds selected from the group consisting of organic acids and amines, and the organic acid has 2 to 29 carbon atoms, preferably carbon. It is preferable that it is 1 type, or 2 or more types of compounds chosen from the group which consists of a compound containing several 3-18 carbons. Specifically, the organic acid is malic acid, citric acid, fumaric acid, maleic acid, tartaric acid, acetic acid, propionic acid, butyric acid, isobutyric acid, vibalic acid, valeric acid, isovaleric acid, caproic acid, 2-ethyl. Butyric acid, caprylic acid, pelargonic acid, 2-ethylhexanoic acid, capric acid, undecanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, arachidic acid, behenic acid, lignoceric acid, serotic acid, montanic acid, It is one or more organic acids selected from the group consisting of melissic acid, ricinoleic acid, 12-hydroxystearic acid, naphthenic acid, abietic acid, dextropimaric acid, palmitoleic acid, oleic acid, linoleic acid and linolenic acid. Preferably malic acid, citric acid, fumaric acid, maleic acid, 2-ethylhexane , Lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, 12-hydroxystearic acid, oleic acid, linoleic acid and linolenic acid may be one or more organic acids preferable. The organic acid is preferably a photopolymerizable compound. Specifically, the photopolymerizable compound preferably contains one or more selected from the group consisting of an acryloyl group, a methacryloyl group, and a vinyl group. Here, the reason why the number of carbon atoms is limited to the range of 2 to 29 is that when the number of carbon atoms is less than 2, a desired organic acid cannot be obtained, and an organic acid having more than 29 carbon atoms is not found and is not substantially used. Because.

  On the other hand, amines are dibutylamine, diisobutylamine, tripentylamine, allylamine, cyclohexylamine, dicyclohexylamine, propylenediamine, diethylenetriamine, dodecylamine, 1,3-dimethyl-n-butylamine, 1-aminoundecane, 1-aminotridecane. Decane, tetradecylamine, hexadecylamine, octadecylamine, oleylamine, dioleylamine, dodecyldimethylamine, tetradecyldimethylamine, hexadecyldimethylamine, octadecyldimethylamine, monoethanolamine, diethanolamine, triethanolamine and 3-methoxypropyl It is preferably one or more selected from the group consisting of amines, and further dibutylamine, dodecylamine, tetra Shiruamin, hexadecylamine, octadecylamine, oleylamine, monoethanolamine, diethanolamine, is preferably one or more amines selected from the group consisting of triethanolamine and 3-methoxypropylamine. The reducing agent is preferably one or more selected from the group consisting of hydrazine, borohydride, dimethylamine borane, formic acid, formate and diphosphite.

  Next, the single substance or the mixture is kept in a predetermined atmosphere with a microwave with an output of 800 to 1250 W, preferably 900 to 1200 W for 3 to 10 minutes, preferably 4 to 8 minutes. As a means for generating this microwave, it is preferable to use a microwave oven, and the frequency of the microwave is set to 2.45 GHz. Moreover, it is preferable that the atmosphere when irradiating a single substance or a mixture with a microwave is an inert gas atmosphere, a reducing gas atmosphere, or an air atmosphere. Here, the microwave output is limited to the range of 800 to 1250 W. If the output is less than 800 W, the generation of the dispersion is insufficient, and if it exceeds 1250 W, the decomposition of the organic matter becomes remarkable, and a stable dispersion cannot be obtained. Because. In addition, the reason for limiting the microwave irradiation time to the range of 3 to 10 minutes is that the dispersion is not sufficiently generated if the time is less than 3 minutes, and if the time exceeds 10 minutes, the reaction proceeds excessively and aggregates are formed. Because. A colloidal dispersion in which particles are dispersed can be produced by such a simple method.

As the particle dispersion produced by the above method, an average particle diameter of 0.005 to 1.0 μm, preferably 0.01 to 0.8 μm of tin oxide, indium oxide, zinc oxide, tin-containing indium oxide (ITO), Zinc-containing indium oxide (IZO), aluminum-containing zinc oxide (AZO), gallium-containing zinc oxide (GZO), cerium-containing zinc oxide (CZO), boron-containing zinc oxide (BZO), antimony-containing tin oxide (ATO), or phosphorus Examples thereof include a particle dispersion containing oxide semiconductor particles of tin oxide (PTO). The oxide semiconductor particles obtained by drying the particle dispersion are tin oxide, indium oxide, zinc oxide, tin having an average particle size of 0.005 to 1.0 μm, preferably 0.01 to 0.8 μm. Containing indium oxide (ITO), zinc containing indium oxide (IZO), aluminum containing zinc oxide (AZO), gallium containing zinc oxide (GZO), cerium containing zinc oxide (CZO), boron containing zinc oxide (BZO), antimony containing oxidation Examples thereof include oxide semiconductor particles of tin (ATO) or phosphorus-containing tin oxide (PTO). Here, the reason why the average particle size of the oxide semiconductor particles is limited to the range of 0.005 to 1.0 μm is that particles having a particle size of less than 0.005 μm or particles exceeding 1.0 μm cannot be obtained by this method. . The average particle size of the oxide semiconductor particles used in the present invention is measured with a laser diffraction / scattering particle size distribution measuring device (LA-950, manufactured by Horiba, Ltd.), and the particle size reference is calculated as the number. 50% average particle diameter (D ₅₀ ). The number-based average particle diameter measured by the laser diffraction / scattering particle size distribution measuring apparatus is the value of any 50 particles in an image observed with a scanning electron microscope (S-4300SE and S-900 manufactured by Hitachi High-Technologies). It almost coincides with the average particle diameter when the particle diameter is actually measured.

<Second Embodiment>
A colloidal dispersion in which particles are dispersed in the same manner as in the first embodiment except that ammonium fluoride is further added to the single or mixture prepared or prepared in the first embodiment. Is made. The particle dispersion produced by this method includes fluorine-containing tin oxide (FTO), fluorine-containing indium oxide (FIO), fluorine having an average particle diameter of 0.005 to 1.0 μm, preferably 0.01 to 0.8 μm. Containing zinc oxide (FZO), fluorine tin containing indium oxide (FITO), fluorine zinc containing indium oxide (FIZO), fluorine aluminum containing zinc oxide (FAZO), fluorine gallium containing zinc oxide (FGZO), fluorine cerium containing zinc oxide (FCZO) ), Or a particle dispersion including oxide semiconductor particles of fluorine antimony-containing tin oxide (FATO). Moreover, as the oxidized particle semiconductor particles obtained by drying the particle dispersion, fluorine-containing tin oxide (FTO) having an average particle diameter of 0.005 to 1.0 μm, preferably 0.01 to 0.8 μm, fluorine-containing Indium oxide (FIO), fluorine-containing zinc oxide (FZO), fluorine tin-containing indium oxide (FITO), fluorine zinc-containing indium oxide (FIZO), fluorine aluminum-containing zinc oxide (FAZO), fluorine gallium-containing zinc oxide (FGZO), Examples thereof include oxide semiconductor particles of fluorine-cerium-containing zinc oxide (FCZO) or fluorine-antimony-containing tin oxide (FATO). Here, the reason why the average particle size of the oxide semiconductor particles is limited to the range of 0.005 to 1.0 μm is that particles having a particle size of less than 0.005 μm or particles exceeding 1.0 μm cannot be obtained by this method. .

In the first and second embodiments, a particle dispersion containing oxide semiconductor particles is manufactured. However, Cu having an average particle diameter of 0.005 to 1.0 μm, preferably 0.01 to 0.8 μm. , Au, Ag, Pt, Pd, Ru, Rh, Re, Fe, Co, Ni, Zn, In and Sn, one or more types of pure metal particles, mixed metal particles or alloy particles A particle dispersion containing In the first and second embodiments, the particle dispersion is dried to produce oxide semiconductor particles. However, the particle dispersion containing the pure metal particles, mixed metal particles, or alloy particles is dried. From Cu, Au, Ag, Pt, Pd, Ru, Rh, Re, Fe, Co, Ni, Zn, In and Sn having an average particle size of 0.005 to 1.0 μm, preferably 0.01 to 0.8 μm Metal particles made of one or more kinds of pure metals, mixed metals or alloys selected from the group may be used. Here, the reason why the average particle diameter of the metal particles is limited to the range of 0.005 to 1.0 μm is that particles having a particle size of less than 0.005 μm or particles exceeding 1.0 μm cannot be obtained by this method.
Moreover, in the said 1st and 2nd embodiment, although the particle dispersion containing an oxide semiconductor particle was manufactured, average particle diameter 0.005-1.0 micrometer, Preferably it is Sb of 0.01-0.8 micrometer. A particle dispersion containing the metalloid particles may be used. Further, in the first and second embodiments, the particle dispersion was dried to produce oxide semiconductor particles, but the particle dispersion containing the Sb semimetal particles was dried to obtain an average particle size of 0. It may be a semi-metal particle composed of 0.005 to 1.0 μm, preferably 0.01 to 0.8 μm of Sb. Here, the reason why the average particle size of the semi-metal particles is limited to the range of 0.005 to 1.0 μm is that particles having a particle size of less than 0.005 μm or particles exceeding 1.0 μm cannot be obtained by this method.

Next, examples of the present invention will be described in detail together with comparative examples.
<Example 1>
First, a soap was prepared by saponifying ethylene oxide-modified succinic acid methacrylate (NK ester SA manufactured by Shin-Nakamura Chemical Co., Ltd.) with sodium hydroxide. This soap was divided into two, and an indium chloride solution (manufactured by Asian Physical Properties) was mixed with one soap and stirred to prepare an indium metal soap. The indium metal soap was sufficiently desalted by washing with water and filtered, and then the desalted indium metal soap was placed in a vacuum dryer at 80 ° C. overnight to dehydrate it, so that the indium soap (carbon Number: 10) was obtained. On the other hand, a tin metal soap was prepared by mixing and stirring a tin chloride solution (manufactured by Asia Physical Properties Co., Ltd.) with the other soap. The tin metal soap was sufficiently desalted by washing with water and filtered, and then the desalted tin metal soap was placed in a vacuum dryer at 80 ° C. overnight and dehydrated to obtain tin soap (carbon Number: 10) was obtained. The chemical formula (1) of the ethylene oxide-modified succinic acid methacrylate is shown here.

次いで図１に示すように、２０ｃｃのガラス瓶に上記インジウム石鹸７．５ｇと錫石鹸０．５ｇとを入れて、気密であって所定のガスを給排可能なグローブボックス１１内に収容された電子レンジ１２のターンテーブル１２ａ上に置いた。次に上記インジウム石鹸と錫石鹸の混合物１３の入ったガラス瓶１４に、直径及び深さがそれぞれ１５０ｍｍ及び７０ｍｍである透明な石英製坩堝１６を被せるとともに、グローブボックス１１内に空気（鈴木商事館社製の一般空気ボンベに貯留された空気）を２００ｃｃ／分ずつ供給しながら電子レンジ１２を出力１０００Ｗで８分間作動させた。その後、上記ガラス瓶１４を電子レンジ１２から取出して室温まで冷却し、コロイド状の粒子分散体１７を得た。この粒子分散体１７を実施例１とした。なお、図１において、符号１２ｂはマイクロ波を発生するマグネトロンであり、符号１２ｃはトランスであり、符号１２ｄは空気を流通させるとともにトランス１２ｃを冷却するファンであり、符号１２ｅはターンテーブル１２ａを回転駆動するモータである。また図１において、破線矢印はマイクロ波の流れを示し、一点鎖線矢印は空気の流れを示す。

Next, as shown in FIG. 1, 7.5 g of the indium soap and 0.5 g of the tin soap are put into a 20 cc glass bottle, and the electrons stored in a glove box 11 that is airtight and can supply and discharge a predetermined gas. It was placed on the turntable 12a of the range 12. Next, the glass bottle 14 containing the mixture 13 of indium soap and tin soap is covered with a transparent quartz crucible 16 having diameters and depths of 150 mm and 70 mm, respectively, and air (Suzuki Corporation) The microwave oven 12 was operated at an output of 1000 W for 8 minutes while supplying 200 cc / min of air stored in a general air cylinder manufactured by the company. Thereafter, the glass bottle 14 was taken out from the microwave oven 12 and cooled to room temperature, whereby a colloidal particle dispersion 17 was obtained. This particle dispersion 17 was designated as Example 1. In FIG. 1, reference numeral 12b is a magnetron that generates microwaves, reference numeral 12c is a transformer, reference numeral 12d is a fan that circulates air and cools the transformer 12c, and reference numeral 12e rotates the turntable 12a. It is a motor to drive. Further, in FIG. 1, broken line arrows indicate the flow of microwaves, and alternate long and short dashed arrows indicate the flow of air.

<Example 2>
First, 7.5 g of indium 12-hydroxystearate (carbon number: 18) and 0.5 g of tin stearate (carbon number: 18) were put in a glass bottle, and 0.3 g of ammonium fluoride was further added to obtain a mixture. . Next, the glass bottle containing the above mixture is put into a microwave oven, and the microwave oven is output at 950 W while supplying air (air stored in a general air cylinder manufactured by Suzuki Shoji Co., Ltd.) at 200 cc / min. Operated for 8 minutes. Thereafter, the glass bottle was taken out from the microwave oven and cooled to room temperature to obtain a colloidal particle dispersion. This particle dispersion was designated as Example 2.
<Example 3>
First, 7.5 g of tin stearate (carbon number: 18) was put in a glass bottle, and 0.3 g of ammonium fluoride was added to obtain a mixture. Next, the glass bottle containing the above mixture is put in a microwave oven, and the microwave oven is output at 850 W while supplying air (air stored in a general air cylinder manufactured by Suzuki Shoji Co., Ltd.) at 200 cc / min. Operated for 8 minutes. Thereafter, the glass bottle was taken out from the microwave oven and cooled to room temperature to obtain a colloidal particle dispersion. This particle dispersion was designated as Example 3.

<Example 4>
First, 7.5 g of indium soap (carbon number: 10 ) was put in a glass bottle, and 0.3 g of ammonium fluoride was added to obtain a mixture. Next, the glass bottle containing the above mixture is put in a microwave oven, and the microwave oven is output at 850 W while supplying air (air stored in a general air cylinder manufactured by Suzuki Shoji Co., Ltd.) at 200 cc / min. Operated for 8 minutes. Thereafter, the glass bottle was taken out from the microwave oven and cooled to room temperature to obtain a colloidal particle dispersion. This particle dispersion was designated as Example 4.
<Example 5>
First, 7.5 g of tin stearate (carbon number: 18) and 0.8 g of montanic acid / 2-aminoethanol antimony complex (carbon number: 29) were put in a glass bottle to obtain a mixture. Next, the glass bottle containing the above mixture is put into a microwave oven, and the microwave oven is output at 1000 W while supplying air (air stored in a general air cylinder manufactured by Suzuki Shoji Co., Ltd.) at 200 cc / min. Operated for 8 minutes. Thereafter, the glass bottle was taken out from the microwave oven and cooled to room temperature to obtain a colloidal particle dispersion. This particle dispersion was designated as Example 5.
<Example 6>
First, 7.5 g of indium oleate (carbon number: 18) and zinc palmitate (carbon number: 16) 0.7 g were put into glass to obtain a mixture. Next, the glass bottle containing the above mixture is put into a microwave oven, and the microwave oven is output at 950 W while supplying air (air stored in a general air cylinder manufactured by Suzuki Shoji Co., Ltd.) at 200 cc / min. Operated for 5 minutes. Thereafter, the glass bottle was taken out from the microwave oven and cooled to room temperature to obtain a colloidal particle dispersion. This particle dispersion was designated as Example 6.

<Example 7>
First, a soap is prepared by saponifying ethylene oxide-modified succinic acid methacrylate (NK ester SA manufactured by Shin-Nakamura Chemical Co., Ltd.) with sodium hydroxide, and then mixing and stirring the soap with an indium chloride solution (manufactured by Asian Physical Properties). Indium metal soap was prepared. The indium metal soap was sufficiently desalted by washing with water and filtered, and then the desalted indium metal soap was placed in a vacuum dryer at 80 ° C. overnight to dehydrate it, so that the indium soap (carbon Number: 10) was obtained. On the other hand, a soap was prepared by saponifying ω-carboxy-polycaprolactone monoacrylate (Aronix M-5300 manufactured by Toagosei Co., Ltd.) with sodium hydroxide, and then mixing the zinc chloride solution with this soap and stirring the zinc. A metal soap was prepared. The zinc metal soap was thoroughly washed with water and filtered for desalting, and then the desalted zinc metal soap was placed in a vacuum dryer at 80 ° C. overnight to dehydrate it to obtain zinc soap (carbon Number: 15) was obtained. The chemical formula (2) of the ω-carboxy-polycaprolactone monoacrylate is shown here.

次いで上記インジウム石鹸７．５ｇと亜鉛石鹸０．７ｇとをガラス瓶に入れて混合物を得た。次に上記混合物の入ったガラス瓶を電子レンジに入れるとともに、グローブボックス内に空気（鈴木商事館社製の一般空気ボンベに貯留された空気）を２００ｃｃ／分ずつ供給しながら電子レンジを出力９５０Ｗで５分間作動させた。その後、上記ガラス瓶を電子レンジから取出して室温まで冷却し、コロイド状の粒子分散体を得た。この粒子分散体を実施例７とした。

Next, 7.5 g of the indium soap and 0.7 g of zinc soap were put in a glass bottle to obtain a mixture. Next, the glass bottle containing the above mixture is put into a microwave oven, and the microwave oven is output at 950 W while supplying air (air stored in a general air cylinder manufactured by Suzuki Shoji Co., Ltd.) at 200 cc / min. Operated for 5 minutes. Thereafter, the glass bottle was taken out from the microwave oven and cooled to room temperature to obtain a colloidal particle dispersion. This particle dispersion was designated as Example 7.

<Example 8>
First, β-carboxyethyl acrylate (β-CEA manufactured by Daicel UCB) was saponified with sodium hydroxide to prepare a soap, and then mixed with a titanium chloride solution and stirred to obtain a titanium metal soap. Was prepared. The titanium metal soap was sufficiently washed with water and filtered to desalinate, and the desalted titanium metal soap was placed in a vacuum dryer at 80 ° C. overnight to dehydrate it to obtain a titanium soap. It was. The chemical formula (3) of the β-carboxyethyl acrylate is shown here.

次いで上記チタン石鹸７．５ｇをガラス瓶に入れた。次にこのチタン石鹸（単一物）の入ったガラス瓶を電子レンジに入れるとともに、グローブボックス内に空気（鈴木商事館社製の一般空気ボンベに貯留された空気）を２００ｃｃ／分ずつ供給しながら電子レンジを出力１２００Ｗで８分間作動させた。その後、上記ガラス瓶を電子レンジから取出して室温まで冷却し、コロイド状の粒子分散体を得た。この粒子分散体を実施例８とした。

Next, 7.5 g of the titanium soap was put in a glass bottle. Next, the glass bottle containing the titanium soap (single item) is put in a microwave oven, and air (air stored in a general air cylinder manufactured by Suzuki Shoji Co., Ltd.) is supplied into the glove box at 200 cc / min. The microwave oven was operated at 1200W output for 8 minutes. Thereafter, the glass bottle was taken out from the microwave oven and cooled to room temperature to obtain a colloidal particle dispersion. This particle dispersion was defined as Example 8.

<Example 9>
First, 7.5 g of titanium coupling agent (KR44, carbon number: 3 and 4 manufactured by Ajinomoto Co., Inc.) is put in a glass bottle. Next, the glass bottle containing the titanium coupling agent (single) is put into a microwave oven, and air (air stored in a general air cylinder manufactured by Suzuki Shoji Co., Ltd.) is supplied 200 cc / min into the glove box. The microwave oven was operated at an output of 1200 W for 5 minutes. Thereafter, the glass bottle was taken out from the microwave oven and cooled to room temperature to obtain a colloidal particle dispersion. This particle dispersion was referred to as Example 9. The chemical formula (4) of the titanium coupling agent (KR44 manufactured by Ajinomoto Co., Inc.) is shown here.

＜実施例１０＞
先ずチタンカップリング剤（味の素社製の９ＳＡ、炭素数：３及び１８）７．５ｇをガラス瓶に入れた。次にこのチタンカップリング剤（単一物）の入ったガラス瓶を電子レンジに入れるとともに、グローブボックス内に空気（鈴木商事館社製の一般空気ボンベに貯留された空気）を２００ｃｃ／分ずつ供給しながら電子レンジを出力１２００Ｗで５分間作動させた。その後、上記ガラス瓶を電子レンジから取出して室温まで冷却し、コロイド状の粒子分散体を得た。この粒子分散体を実施例１０とした。なお、上記チタンカップリング剤（味の素社製の９ＳＡ）の化学式（５）をここに示す。

<Example 10>
First, 7.5 g of a titanium coupling agent (9SA manufactured by Ajinomoto Co., Inc., carbon number: 3 and 18) was put in a glass bottle. Next, the glass bottle containing the titanium coupling agent (single) is put into a microwave oven, and air (air stored in a general air cylinder manufactured by Suzuki Shoji Co., Ltd.) is supplied 200 cc / min into the glove box. The microwave oven was operated at an output of 1200 W for 5 minutes. Thereafter, the glass bottle was taken out from the microwave oven and cooled to room temperature to obtain a colloidal particle dispersion. This particle dispersion was designated as Example 10. The chemical formula (5) of the titanium coupling agent (9SA manufactured by Ajinomoto Co., Inc.) is shown here.

＜比較例１＞
先ずオレイン酸インジウム（炭素数：１８）７．５ｇとステアリン酸錫（炭素数：１８）０．５ｇとをガラス瓶に入れて混合物を得た。次に上記混合物の入ったガラス瓶を電子レンジに入れるとともに、グローブボックス内に空気（鈴木商事館社製の一般空気ボンベに貯留された空気）を２００ｃｃ／分ずつ供給しながら電子レンジを出力１３００Ｗで６分間作動させた。その後、上記ガラス瓶を電子レンジから取出して室温まで冷却し、コロイド状の粒子分散体を得た。この粒子分散体を比較例１とした。
＜比較例２＞
先ずオレイン酸インジウム（炭素数：１８）７．５ｇとステアリン酸錫（炭素数：１８）０．５ｇとをガラス瓶に入れて混合物を得た。次に上記混合物の入ったガラス瓶を電子レンジに入れるとともに、グローブボックス内に空気（鈴木商事館社製の一般空気ボンベに貯留された空気）を２００ｃｃ／分ずつ供給しながら電子レンジを出力１０００Ｗで１１分間作動させた。その後、上記ガラス瓶を電子レンジから取出して室温まで冷却し、コロイド状の粒子分散体を得た。この粒子分散体を比較例２とした。
＜比較例３＞
先ずオレイン酸インジウム（炭素数：１８）７．５ｇとステアリン酸錫（炭素数：１８）０．５ｇとをガラス瓶に入れて混合物を得た。次に上記混合物の入ったガラス瓶を電子レンジに入れるとともに、グローブボックス内に空気（鈴木商事館社製の一般空気ボンベに貯留された空気）を２００ｃｃ／分ずつ供給しながら電子レンジを出力７５０Ｗで４分間作動させた。その後、上記ガラス瓶を電子レンジから取出して室温まで冷却し、コロイド状の粒子分散体を得た。この粒子分散体を比較例３とした。

<Comparative Example 1>
First, 7.5 g of indium oleate (carbon number: 18) and 0.5 g of tin stearate (carbon number: 18) were put in a glass bottle to obtain a mixture. Next, the glass bottle containing the above mixture is put into a microwave oven, and the microwave oven is output at 1300 W while supplying air (air stored in a general air cylinder manufactured by Suzuki Shoji Co., Ltd.) at 200 cc / min. Run for 6 minutes. Thereafter, the glass bottle was taken out from the microwave oven and cooled to room temperature to obtain a colloidal particle dispersion. This particle dispersion was designated as Comparative Example 1.
<Comparative Example 2>
First, 7.5 g of indium oleate (carbon number: 18) and 0.5 g of tin stearate (carbon number: 18) were put in a glass bottle to obtain a mixture. Next, the glass bottle containing the above mixture is put into a microwave oven, and the microwave oven is output at 1000 W while supplying air (air stored in a general air cylinder manufactured by Suzuki Shoji Co., Ltd.) at 200 cc / min. Operated for 11 minutes. Thereafter, the glass bottle was taken out from the microwave oven and cooled to room temperature to obtain a colloidal particle dispersion. This particle dispersion was designated as Comparative Example 2.
<Comparative Example 3>
First, 7.5 g of indium oleate (carbon number: 18) and 0.5 g of tin stearate (carbon number: 18) were put in a glass bottle to obtain a mixture. Next, the glass bottle containing the above mixture is put into a microwave oven, and the microwave oven is output at 750 W while supplying air (air stored in a general air cylinder manufactured by Suzuki Shoji Co., Ltd.) at 200 cc / min. Operated for 4 minutes. Thereafter, the glass bottle was taken out from the microwave oven and cooled to room temperature to obtain a colloidal particle dispersion. This particle dispersion was designated as Comparative Example 3.

<Comparative Example 4>
First, 7.5 g of indium oleate (carbon number: 18) and 0.5 g of tin stearate (carbon number: 18) were put in a glass bottle to obtain a mixture. Next, the glass bottle containing the above mixture is put into a microwave oven, and the microwave oven is output at 800 W while supplying air (air stored in a general air cylinder manufactured by Suzuki Shoji Co., Ltd.) at 200 cc / min. Run for 2 minutes. Thereafter, the glass bottle was taken out from the microwave oven and cooled to room temperature to obtain a colloidal particle dispersion. This particle dispersion was designated as Comparative Example 4.
<Comparative Example 5>
First, 7.5 g of indium oleate (carbon number: 18) and 0.5 g of tin stearate (carbon number: 18) are put in a glass bottle, and methyl carbitol (abbreviation: MCT) is added as a solvent to obtain a mixture. It was. Next, the glass bottle containing the above mixture is put in a microwave oven, and the microwave oven is output at 850 W while supplying air (air stored in a general air cylinder manufactured by Suzuki Shoji Co., Ltd.) at 200 cc / min. Operated for 8 minutes. Thereafter, the glass bottle was taken out from the microwave oven and cooled to room temperature to obtain a colloidal particle dispersion. This particle dispersion was designated as Comparative Example 5.

<Comparative test 1 and evaluation>
After the particle dispersions of Examples 1 to 10 and Comparative Examples 1 to 5 were washed with acetone, the powders were held in a vacuum atmosphere at room temperature for 2 hours to produce dry powders composed of metal or metalloid compound particles, and X-ray diffraction The compound constituting the dry powder is identified by the XRD method (XRD method), the pattern (crystal structure) and name of the compound is specified, and the elemental analysis of the dry powder is performed by X-ray fluorescence spectrometry (XFS method) Then, the average particle diameter of the primary particles of the dry powder was determined by a transmission electron microscope (TEM). The results are shown in Table 1. In Table 1, “MCT” in Comparative Example 5 is methyl carbitol.

表１から明らかなように、比較例３及び４では未反応部分が多く、比較例５では原料粉末の有機金属化合物と変わっていなかった。これに対し、実施例１、２、４、６及び７では乾燥粉末の金属又は半金属化合物粒子のパターン（結晶構造）がビックスバイト（bixbite）型構造であり、実施例３及び５では乾燥粉末の金属又は半金属化合物粒子のパターン（結晶構造）がルチル（rutile）型構造であり、実施例８〜１０では乾燥粉末の金属又は半金属化合物粒子のパターン（結晶構造）がアナターゼ（anataze）型構造であった。また実施例１〜１０では、乾燥粉末の金属又は半金属化合物粒子がＩｎ、Ｓｎ、Ｓｂ等の金属又は半金属を含んでおり、金属又は半金属化合物粒子の一次粒子の平均粒径が４〜１０ｎｍと極めて微細であることが分かった。なお、比較例１及び２では乾燥粉末の金属化合物粒子のパターン（結晶構造）がビックスバイト（bixbite）型構造であり、金属化合物粒子の平均粒径がそれぞれ１４ｎｍ及び１１ｎｍと比較的微細であったが、後述する比較試験２に示すように沈殿してしまい、分散液が得られなかった。

As is clear from Table 1, Comparative Examples 3 and 4 had many unreacted parts, and Comparative Example 5 was not different from the organometallic compound of the raw material powder. In contrast, in Examples 1, 2, 4, 6 and 7, the pattern (crystal structure) of the metal or metalloid compound particles of the dry powder is a bixbite type structure, and in Examples 3 and 5, the dry powder The pattern (crystal structure) of the metal or metalloid compound particles is a rutile structure, and in Examples 8 to 10, the pattern (crystal structure) of the metal or metalloid compound particles of the dry powder is an anatase type. It was a structure. Moreover, in Examples 1-10, the metal or metalloid compound particle | grains of dry powder contain metals or metalloids, such as In, Sn, Sb, and the average particle diameter of the primary particle of metal or metalloid compound particle | grains is 4- It was found to be extremely fine as 10 nm. In Comparative Examples 1 and 2, the pattern (crystal structure) of the metal compound particles of the dry powder was a bixbite type structure, and the average particle diameters of the metal compound particles were relatively fine as 14 nm and 11 nm, respectively. However, as shown in the comparative test 2 mentioned later, it settled and the dispersion liquid was not obtained.

<Example 11>
The particle dispersion of Example 1 was diluted with 2-isopropoxyethanol (solvent, abbreviation: isoPG), then washed and concentrated by an ultrafiltration method so that the particle content was about 30% by weight. The body was prepared. This particle dispersion was designated as Example 11.
<Example 12>
After the particle dispersion of Example 2 was diluted with methyl carbitol (solvent, abbreviation: MCT), the particle dispersion was washed and concentrated by an ultrafiltration method so that the particle content was about 30% by weight. Prepared. This particle dispersion was designated as Example 12.
<Example 13>
The particle dispersion of Example 3 was diluted with isopropanol (solvent, abbreviation: IPA), then washed and concentrated by an ultrafiltration method to prepare a particle dispersion so that the particle content was about 30% by weight. . This particle dispersion was designated as Example 13.
<Example 14>
The particle dispersion of Example 4 was diluted with isopropanol (solvent, abbreviation: IPA), then washed and concentrated by an ultrafiltration method to prepare a particle dispersion so that the particle content was about 30% by weight. . This particle dispersion was designated as Example 14.
<Example 15>
The particle dispersion of Example 5 was diluted with isopropanol (solvent, abbreviation: IPA), then washed and concentrated by an ultrafiltration method to prepare a particle dispersion so that the particle content was about 30% by weight. . This particle dispersion was designated as Example 15.

<Example 16>
The particle dispersion of Example 6 was diluted with N-methylpyrrolidone (solvent, abbreviation: NMP), then washed and concentrated by an ultrafiltration method so that the particle content was about 30% by weight. Was prepared. This particle dispersion was designated as Example 16.
<Example 17>
The particle dispersion of Example 7 was diluted with hexane (solvent, abbreviation: Hx), then washed and concentrated by an ultrafiltration method to prepare a particle dispersion so that the particle content was about 30% by weight. . This particle dispersion was designated as Example 17.
<Example 18>
After the particle dispersion of Example 8 was diluted with propylene glycol monomethyl ether acetate (solvent, abbreviation: PGMEA), it was washed and concentrated by an ultrafiltration method so that the particle content was about 30% by weight. The body was prepared. This particle dispersion was designated as Example 18.
<Example 19>
The particle dispersion of Example 9 was diluted with propylene glycol monomethyl ether (solvent, abbreviation: PGM), then washed and concentrated by an ultrafiltration method so that the particle content was about 30% by weight. Was prepared. This particle dispersion was designated as Example 19.
<Example 20>
After the particle dispersion of Example 10 was diluted with propylene glycol monomethyl ether acetate (solvent, abbreviation: PGMEA), it was washed and concentrated by an ultrafiltration method so that the particle content was about 30% by weight. The body was prepared. This particle dispersion was designated as Example 20.

<Comparative Example 6>
After the particle dispersion of Comparative Example 1 was diluted with methyl carbitol (solvent, abbreviation: MCT), the particle dispersion was washed and concentrated by an ultrafiltration method so that the particle content was about 30% by weight. Prepared. This particle dispersion was designated as Comparative Example 6.
<Comparative Example 7>
After the particle dispersion of Comparative Example 2 was diluted with methyl carbitol (solvent, abbreviation: MCT), the particle dispersion was washed and concentrated by an ultrafiltration method so that the particle content was about 30% by weight. Prepared. This particle dispersion was designated as Comparative Example 7.
<Comparative Example 8>
After the particle dispersion of Comparative Example 3 was diluted with methyl carbitol (solvent, abbreviation: MCT), the particle dispersion was washed and concentrated by an ultrafiltration method so that the particle content was about 30% by weight. Prepared. This particle dispersion was designated as Comparative Example 8.
<Comparative Example 9>
After the particle dispersion of Comparative Example 4 was diluted with methyl carbitol (solvent, abbreviation: MCT), the particle dispersion was washed and concentrated by an ultrafiltration method so that the particle content was about 30% by weight. Prepared. This particle dispersion was designated as Comparative Example 9.

<Comparative test 2 and evaluation>
The state of the particle dispersion immediately after washing and concentration to about 30% by weight of Examples 11 to 20 and Comparative Examples 6 to 9 and the state after being kept in a sealed glass bottle at 40 ° C. for 2 weeks are visually observed. Observed. The results are shown in Table 2. In Table 2, “isoPG” is an abbreviation for 2-isopropoxyethanol, “MCT” is an abbreviation for methyl carbitol, “IPA” is an abbreviation for isopropanol, and “NMP” is an abbreviation for N-methylpyrrolidone. “Hx” is an abbreviation for hexane, “PGMEA” is an abbreviation for propylene glycol monomethyl ether acetate, and “PGM” is an abbreviation for propylene glycol monomethyl ether.

表２から明らかなように、比較例６〜９では２週間後いずれも沈殿していたのに対し、実施例１１〜２０では２週間後も沈殿せずコロイド特有のインク状態のままであった。この結果、上記実施例のような簡便な方法で、特別な分散装置を使用せずに、高濃度の金属又は半金属化合物粒子の分散した粒子分散体（コロイド液）が比較的容易に製造できることが判った。

As is apparent from Table 2, in Comparative Examples 6 to 9, all were precipitated after 2 weeks, while in Examples 11 to 20, they were not precipitated after 2 weeks and remained in the ink state peculiar to the colloid. . As a result, a particle dispersion (colloid liquid) in which high-concentration metal or metalloid compound particles are dispersed can be produced relatively easily by a simple method as in the above-described embodiment, without using a special dispersion apparatus. I understood.

<Example 21>
First, 0.7 g of copper isostearate (carbon number: 18) was put in a glass bottle. Next, the glass bottle containing the copper isostearate (single product) was put into a microwave oven, and the microwave oven was operated at an output of 1000 W for 8 minutes while supplying nitrogen gas into the glove box at 200 cc / min. Thereafter, the glass bottle was taken out from the microwave oven and cooled to room temperature to obtain a colloidal particle dispersion. This particle dispersion was designated as Example 21.
<Example 22>
First, 0.7 g of silver caproate (carbon number: 6) was put in a glass bottle. Next, the glass bottle containing the silver caproate (single item) was put into a microwave oven, and the microwave oven was operated at an output of 850 W for 5 minutes while supplying nitrogen gas into the glove box at 200 cc / min. Thereafter, the glass bottle was taken out from the microwave oven and cooled to room temperature to obtain a colloidal particle dispersion. This particle dispersion was designated as Example 22.

<Example 23>
First, 0.35 g of silver oleate (carbon number: 18) and 0.35 g of palladium 2-ethylhexanoate (carbon number: 8) were put in a glass bottle to obtain a mixture. Next, the glass bottle containing the mixture was put in a microwave oven, and the microwave oven was operated at an output of 850 W for 5 minutes while supplying nitrogen gas into the glove box at 200 cc / min. Thereafter, the glass bottle was taken out from the microwave oven and cooled to room temperature to obtain a colloidal particle dispersion. This particle dispersion was designated as Example 23.
<Example 24>
First, 0.7 g of palladium 2-ethylhexanoate (carbon number: 8) was put in a glass bottle. Next, the glass bottle containing this palladium 2-ethylhexanoate (single item) is put in a microwave oven, and the microwave oven is operated at an output of 850 W for 5 minutes while supplying 200 cc / min of nitrogen gas into the glove box. It was. Thereafter, the glass bottle was taken out from the microwave oven and cooled to room temperature to obtain a colloidal particle dispersion. This particle dispersion was designated as Example 24.

<Example 25>
First, 0.7 g of caproic acid / 2-ethylhexylamine gold complex (carbon number: 6, 8) was put in a glass bottle. Next, the caproic acid / 2-ethylhexylamine gold complex (single substance) was put in a microwave oven, and the microwave oven was operated at an output of 1000 W for 5 minutes while supplying 200 cc / min of nitrogen gas into the glove box. Thereafter, the glass bottle was taken out from the microwave oven and cooled to room temperature to obtain a colloidal particle dispersion. This particle dispersion was designated as Example 25.
<Example 26>
First, 0.6 g of oleic acid / propylenediamine gold complex (carbon number: 18, 3) and 0.1 g of copper isostearate (carbon number: 18) were put in a glass bottle to obtain a mixture. Next, the glass bottle containing the mixture was placed in a microwave oven, and the microwave oven was operated at an output of 1000 W for 8 minutes while supplying 200 cc / min of nitrogen gas into the glove box. Thereafter, the glass bottle was taken out from the microwave oven and cooled to room temperature to obtain a colloidal particle dispersion. This particle dispersion was designated as Example 26.

<Example 27>
First, 0.7 g of oleylamine platinum complex (carbon number: 18) was put in a glass bottle. Next, the glass bottle containing the oleylamine platinum complex (single substance) was put in a microwave oven, and the microwave oven was operated at an output of 850 W for 8 minutes while supplying 200 cc / min of nitrogen gas into the glove box. Thereafter, the glass bottle was taken out from the microwave oven and cooled to room temperature to obtain a colloidal particle dispersion. This particle dispersion was designated as Example 27.
<Example 28>
First, 0.7 g of ruthenium vibalate (carbon number: 5) was put in a glass bottle. Next, the glass bottle containing the ruthenium vibalate (single substance) was put into a microwave oven, and the microwave oven was operated at an output of 1200 W for 8 minutes while supplying 200 cc / min of nitrogen gas into the glove box. Thereafter, the glass bottle was taken out from the microwave oven and cooled to room temperature to obtain a colloidal particle dispersion. This particle dispersion was designated as Example 28.

<Example 29>
First, 0.3 g of iron stearate (carbon number: 18), cobalt acetate (carbon number: 2) 0.1 g and nickel behenate (carbon number: 22) 0.3 g were put in a glass bottle to obtain a mixture. Next, the glass bottle containing the mixture was placed in a microwave oven, and the microwave oven was operated at an output of 1200 W for 8 minutes while supplying nitrogen gas into the glove box at 200 cc / min. Thereafter, the glass bottle was taken out from the microwave oven and cooled to room temperature to obtain a colloidal particle dispersion. This particle dispersion was designated as Example 29.
<Example 30>
First, 0.7 g of linoleic acid / tetradecylamine rhodium complex (carbon number: 18, 14) was put in a glass bottle. Next, a glass bottle containing linoleic acid / tetradecylamine rhodium complex (single) is put into a microwave oven, and nitrogen gas is supplied into the glove box at 200 cc / min. I let you. Thereafter, the glass bottle was taken out from the microwave oven and cooled to room temperature to obtain a colloidal particle dispersion. This particle dispersion was designated as Example 30.

<Example 31>
First, 0.7 g of linolenic acid / hexadecylamine rhenium complex (carbon number: 18, 16) was put in a glass bottle. Next, the glass bottle containing the linolenic acid / hexadecylamine rhenium complex (single) is put into a microwave oven, and nitrogen gas is supplied into the glove box at 200 cc / min. Activated. Thereafter, the glass bottle was taken out from the microwave oven and cooled to room temperature to obtain a colloidal particle dispersion. This particle dispersion was designated as Example 31.
<Example 32>
First, 0.65 g of indium oleate (carbon number: 18) and 0.5 g of dodecylamine tin complex (carbon number: 12) were put in a glass bottle to obtain a mixture. Next, the glass bottle containing the mixture was placed in a microwave oven, and the microwave oven was operated for 9 minutes at an output of 1000 W while supplying nitrogen gas into the glove box at 200 cc / min. Thereafter, the glass bottle was taken out from the microwave oven and cooled to room temperature to obtain a colloidal particle dispersion. This particle dispersion was defined as Example 32.

<Example 33>
First, 0.6 g of indium 12-hydroxystearate (carbon number: 18) and 0.1 g of zinc palmitate (carbon number: 16) were put in a glass bottle to obtain a mixture. Next, the glass bottle containing the mixture was put into a microwave oven, and the microwave oven was operated at an output of 850 W for 9 minutes while supplying nitrogen gas into the glove box at 200 cc / min. Thereafter, the glass bottle was taken out from the microwave oven and cooled to room temperature to obtain a colloidal particle dispersion. This particle dispersion was designated as Example 33.
<Example 34>
First, 0.7 g of silver acrylate (carbon number: 4) was put in a glass bottle. Next, the glass bottle containing the silver acrylate (single) was put into a microwave oven, and the microwave oven was operated at an output of 850 W for 5 minutes while supplying nitrogen gas into the glove box at 200 cc / min. Thereafter, the glass bottle was taken out from the microwave oven and cooled to room temperature to obtain a colloidal particle dispersion. This particle dispersion was designated as Example 34.

<Example 35>
First, 0.35 g of silver methacrylate (carbon number: 5 ) and 0.35 g of palladium acrylate (carbon number: 4) were put in a glass bottle to obtain a mixture. Next, the glass bottle containing the mixture was placed in a microwave oven, and the microwave oven was operated at an output of 850 W for 5 minutes while supplying 200 cc / min of nitrogen gas into the glove box. Thereafter, the glass bottle was taken out from the microwave oven and cooled to room temperature to obtain a colloidal particle dispersion. This particle dispersion was designated as Example 35.
<Example 36>
0.65 g of indium soap (carbon number: 10) of Example 1 and 0.5 g of tin soap (carbon number: 10) of Example 1 were put in a glass bottle to obtain a mixture. Next, the glass bottle containing the mixture was put into a microwave oven, and the microwave oven was operated at an output of 1100 W for 9 minutes while supplying nitrogen gas into the glove box at 200 cc / min. Thereafter, the glass bottle was taken out from the microwave oven and cooled to room temperature to obtain a colloidal particle dispersion. This particle dispersion was designated as Example 36.

<Example 37>
First, a soap was prepared by saponifying ethylene oxide-modified succinic acid methacrylate (NK ester SA, manufactured by Shin-Nakamura Chemical Co., Ltd.) with sodium hydroxide, and then mixing the gold chloride solution with the soap and stirring the gold metal soap. Prepared. Next, the gold metal soap was sufficiently washed with water and filtered for desalting, and then the desalted gold metal soap was placed in a vacuum dryer at 80 ° C. overnight to dehydrate it to dehydrate the gold soap ( Carbon number: 10) was obtained. Next, 0.7 g of this gold soap was put in a glass bottle. Further, the glass bottle containing the gold soap (single item) was put into a microwave oven, and the microwave oven was operated at an output of 1000 W for 5 minutes while supplying nitrogen gas into the glove box at 200 cc / min. Thereafter, the glass bottle was taken out from the microwave oven and cooled to room temperature to obtain a colloidal particle dispersion. This particle dispersion was designated as Example 37.
<Example 38>
First, 0.7 g of platinum methacrylate (carbon number: 5) was put in a glass bottle. Next, the glass bottle containing platinum methacrylate (single) was put into a microwave oven, and the microwave oven was operated at an output of 1000 W for 5 minutes while supplying 200 cc / min of nitrogen gas into the glove box. Thereafter, the glass bottle was taken out from the microwave oven and cooled to room temperature to obtain a colloidal particle dispersion. This particle dispersion was designated as Example 38.

<Comparative Example 10>
First, 0.7 g of silver caproate (carbon number: 6) was put in a glass bottle. Next, the glass bottle containing the silver caproate (single item) was put into a microwave oven, and the microwave oven was operated at an output of 1300 W for 6 minutes while supplying 200 cc / min of nitrogen gas into the glove box. Thereafter, the glass bottle was taken out from the microwave oven and cooled to room temperature to obtain a colloidal particle dispersion. This particle dispersion was designated as Comparative Example 10.
<Comparative Example 11>
First, 0.7 g of silver caproate (carbon number: 6) was put in a glass bottle. Next, the glass bottle containing the silver caproate (single item) was put into a microwave oven, and the microwave oven was operated at an output of 1000 W for 11 minutes while supplying nitrogen gas into the glove box at 200 cc / min. Thereafter, the glass bottle was taken out from the microwave oven and cooled to room temperature to obtain a colloidal particle dispersion. This particle dispersion was designated as Comparative Example 11.
<Comparative Example 12>
First, 0.7 g of silver caproate (carbon number: 6) was put in a glass bottle. Next, the glass bottle containing the silver caproate (single item) was put in a microwave oven, and the microwave oven was operated at an output of 750 W for 4 minutes while supplying nitrogen gas into the glove box at 200 cc / min. Thereafter, the glass bottle was taken out from the microwave oven and cooled to room temperature to obtain a colloidal particle dispersion. This particle dispersion was designated as Comparative Example 12.
<Comparative Example 13>
First, 0.7 g of silver caproate (carbon number: 6) was put in a glass bottle. Next, the glass bottle containing the silver caproate (single item) was put into a microwave oven, and the microwave oven was operated at an output of 800 W for 2 minutes while supplying nitrogen gas into the glove box at 200 cc / min. Thereafter, the glass bottle was taken out from the microwave oven and cooled to room temperature to obtain a colloidal particle dispersion. This particle dispersion was designated as Comparative Example 13.

<Comparative example 14>
First, 0.7 g of silver caproate (carbon number: 6) was put in a glass bottle, and 1.5 g of decalin (solvent) was added to obtain a mixture. Next, the glass bottle containing the above mixture was put into a microwave oven, and the microwave oven was operated at an output of 850 W for 8 minutes while supplying nitrogen gas into the glove box at 200 cc / min. Thereafter, the glass bottle was taken out from the microwave oven and cooled to room temperature to obtain a colloidal particle dispersion. This particle dispersion was designated as Comparative Example 14.
<Comparative test 3 and evaluation>
After the particle dispersions of Examples 21 to 38 and Comparative Examples 9 to 14 were washed with acetone, they were kept in a vacuum atmosphere at room temperature for 2 hours to produce dry powders composed of metal particles, and X-ray photoelectron spectroscopy (XPS) The compound constituting the dry powder is identified by the method) to determine the oxidation number of the compound, and elemental analysis of the dry powder is performed by a field emission transmission electron microscope (FE-TEM). The average particle size was determined. The results are shown in Tables 3 and 4.

表３及び表４から明らかなように、比較例１０では銀メタルの凝集塊が発生し、比較例１１では酸化数がゼロであったけれども金属粒子の一次粒子の平均粒径がミクロンオーダと大きく、比較例１２では反応部分が多く、更に比較例１３及び１４では原料粉末の有機金属化合物と変わっていなかった。これに対し、実施例２１〜３８では乾燥粉末の金属粒子の酸化数がゼロであり、また実施例２１〜３８では、乾燥粉末の金属粒子がＩｎ、Ｓｎ等の金属を含み、更に金属粒子の一次粒子の平均粒径が２〜１３ｎｍと極めて微細であることが分かった。

As apparent from Tables 3 and 4, in Comparative Example 10, silver metal agglomerates were generated. In Comparative Example 11, although the oxidation number was zero, the average particle size of the primary particles of the metal particles was as large as micron. In Comparative Example 12, there were many reaction parts, and in Comparative Examples 13 and 14, the organometallic compound of the raw material powder was not changed. On the other hand, in Examples 21 to 38, the oxidation number of the metal particles of the dry powder is zero, and in Examples 21 to 38, the metal particles of the dry powder contain a metal such as In and Sn, and It turned out that the average particle diameter of a primary particle is very fine with 2-13 nm.

<Example 39>
After the particle dispersion of Example 21 was diluted with toluene (solvent, abbreviation: TL), it was washed and concentrated by an ultrafiltration method to prepare a particle dispersion so that the particle content was about 40% by weight. . This particle dispersion was referred to as Example 39.
<Example 40>
The particle dispersion of Example 22 was diluted with isopropanol (solvent, abbreviation: IPA), then washed and concentrated by an ultrafiltration method to prepare a particle dispersion so that the particle content was about 40% by weight. . This particle dispersion was designated as Example 40.
<Example 41>
The particle dispersion of Example 23 was diluted with 2-isopropoxyethanol (solvent, abbreviation: isoPG), washed and concentrated by an ultrafiltration method so that the particle content was about 40% by weight. The body was prepared. This particle dispersion was defined as Example 41.
<Example 42>
The particle dispersion of Example 24 was diluted with isopropanol (solvent, abbreviation: IPA), then washed and concentrated by an ultrafiltration method to prepare a particle dispersion so that the particle content was about 40% by weight. . This particle dispersion was designated as Example 42.
<Example 43>
The particle dispersion of Example 25 was diluted with isopropanol (solvent, abbreviation: IPA), then washed and concentrated by an ultrafiltration method to prepare a particle dispersion so that the particle content was about 40% by weight. . This particle dispersion was designated as Example 43.

<Example 44>
After the particle dispersion of Example 26 was diluted with α-terpineol (solvent, abbreviation: TP), the particle dispersion was washed and concentrated by an ultrafiltration method so that the particle content was about 40% by weight. Prepared. This particle dispersion was designated as Example 44.
<Example 45>
After the particle dispersion of Example 27 was diluted with α-terpineol (solvent, abbreviation: TP), the particle dispersion was washed and concentrated by an ultrafiltration method so that the particle content was about 40% by weight. Prepared. This particle dispersion was defined as Example 45.
<Example 46>
The particle dispersion of Example 28 was diluted with water (solvent, abbreviation: W), then washed and concentrated by an ultrafiltration method to prepare a particle dispersion so that the particle content was about 40% by weight. . This particle dispersion was designated as Example 46.
<Example 47>
The particle dispersion of Example 29 was diluted with propylene glycol monomethyl ether (solvent, abbreviation: PGM), washed and concentrated by an ultrafiltration method so that the particle content was about 40% by weight. Was prepared. This particle dispersion was designated as Example 47.
<Example 48>
The particle dispersion of Example 30 was diluted with hexane (solvent, abbreviation: Hx), then washed and concentrated by an ultrafiltration method to prepare a particle dispersion so that the particle content was about 40% by weight. . This particle dispersion was designated as Example 48.

<Example 49>
After the particle dispersion of Example 31 was diluted with methyl carbitol (solvent, abbreviation: MCT), the particle dispersion was washed and concentrated by an ultrafiltration method so that the particle content was about 40% by weight. Prepared. This particle dispersion was designated as Example 49.
<Example 50>
The particle dispersion of Example 32 was diluted with decalin (solvent, abbreviation: DC), then washed and concentrated by ultrafiltration to prepare a particle dispersion so that the particle content was about 40% by weight. . This particle dispersion was designated as Example 50.
<Example 51>
The particle dispersion of Example 33 was diluted with decalin (solvent, abbreviation: DC), then washed and concentrated by ultrafiltration to prepare a particle dispersion so that the particle content was about 40% by weight. . This particle dispersion was designated as Example 51.
<Example 52>
The particle dispersion of Example 34 was diluted with isopropanol (solvent, abbreviation: IPA), then washed and concentrated by an ultrafiltration method to prepare a particle dispersion so that the particle content was about 40% by weight. . This particle dispersion was designated as Example 52.
<Example 53>
The particle dispersion of Example 35 was diluted with isopropanol (solvent, abbreviation: IPA), then washed and concentrated by an ultrafiltration method to prepare a particle dispersion so that the particle content was about 40% by weight. . This particle dispersion was designated as Example 53.

<Example 54>
The particle dispersion of Example 36 was diluted with tetradecane (solvent, abbreviation: TD), then washed and concentrated by an ultrafiltration method to prepare a particle dispersion so that the particle content was about 40% by weight. . This particle dispersion was designated as Example 54.
<Example 55>
The particle dispersion of Example 37 was diluted with hexane (solvent, abbreviation: Hx), then washed and concentrated by an ultrafiltration method to prepare a particle dispersion so that the particle content was about 40% by weight. . This particle dispersion was defined as Example 55.
<Example 56>
After the particle dispersion of Example 38 was diluted with propylene glycol monomethyl ether acetate (solvent, abbreviation: PGMEA), it was washed and concentrated by an ultrafiltration method so that the particle content was about 40% by weight. The body was prepared. This particle dispersion was designated as Example 56.
<Comparative Example 15>
The particle dispersion of Comparative Example 11 was mixed with isopropanol (solvent, abbreviation: IPA). This mixture was designated as Comparative Example 15.

<Comparative test 4 and evaluation>
The state of the particle dispersion immediately after being washed and concentrated to about 30% by weight of the mixture of the particle dispersions of Examples 39 to 56 and Comparative Example 15, and after being kept in a sealed glass bottle at 40 ° C. for 2 weeks The state was observed visually. The results are shown in Tables 5 and 6. In Tables 5 and 6, “TL” is an abbreviation for toluene, “IPA” is an abbreviation for isopropanol, “isoPG” is an abbreviation for 2-isopropoxyethanol, and “TP” is an abbreviation for α-terpineol. “W” is an abbreviation for water, “PGM” is an abbreviation for propylene glycol monomethyl ether, “Hx” is an abbreviation for hexane, “MCT” is an abbreviation for methyl carbitol, and “DC "Is an abbreviation for decalin," TD "is an abbreviation for tetradecane, and" PGMEA "is an abbreviation for propylene glycol monomethyl ether acetate.

表５及び表６から明らかなように、比較例１５ではイソプロパノール（溶媒、略称：ＩＰＡに全く分散しなかったのに対し、実施例３９〜５６では２週間後も沈殿せずコロイド特有のインク状態のままであった。この結果、上記実施例のような簡便な方法で、特別な分散装置を使用せずに、高濃度の金属粒子の分散した粒子分散体（コロイド液）が比較的容易に製造できることが判った。

As apparent from Tables 5 and 6, in Comparative Example 15, it was not dispersed at all in isopropanol (solvent, abbreviation: IPA), whereas in Examples 39 to 56, the ink state peculiar to the colloid was not precipitated after 2 weeks. As a result, a particle dispersion (colloidal liquid) in which high-concentration metal particles are dispersed can be relatively easily performed by a simple method as in the above-described embodiment, without using a special dispersing apparatus. It was found that it could be manufactured.

<Example 57>
First, the particle dispersion of Example 11 (dispersion in which ITO particles having a concentration of about 30% by weight are dispersed) is diluted with ethanol so that the content of ITO particles becomes 4.0% by weight. A particle dispersion was prepared by dissolving 0.1% by weight of photoinitiator (Irgacure 500 manufactured by Ciba Specialty Chemicals) into the body. Next, the diluted soda glass plate (length 100 mm, width 100 mm, thickness 2.8 mm) is kept at 40 ° C., and this diluted and prepared particle is rotated with a spin coater at a speed of 150 rpm. 5 cc of the dispersion was dropped and shaken for 120 seconds to prepare a film.
A stainless steel photomask 31 (FIG. 2) was placed on a glass plate with the film facing upward. This photomask 31 is formed in a square shape with a length × width × thickness of 100 mm × 100 mm × 1.0 mm, respectively, and three rectangular window holes 31a each having a width × length of 20 mm × 50 mm are formed at intervals of 10 mm. Is done. Next, after irradiating UV energy of 250 mJ / cm ² from above the glass plate with an ultraviolet irradiation device (160 W metal halide lamp: distance 10 cm), the glass plate from which the photomask has been removed is placed on a hot plate and brought to 100 ° C. in the atmosphere. Hold for 10 minutes. Next, the glass plate is rinsed with an ethanol solution in which 10% by weight of N, N-dimethylformamide and 5% by weight of acetylacetone are mixed to dissolve the film of the non-light-irradiated portion, leaving only the light-irradiated film. A patterned film having the same shape as the rectangular window hole of the photomask was obtained. Further, this glass plate was held at 220 ° C. for 30 minutes in a nitrogen gas atmosphere to fire the film, and then cooled to room temperature. This glass plate was referred to as Example 57.

<Example 58>
A glass plate was produced in the same manner as in Example 57, except that the particle dispersion of Example 17 (dispersion in which IZO particles having a concentration of about 30% by weight were dispersed) was used. This glass plate was referred to as Example 58.

<Comparative test 5 and evaluation>
The thickness of the glass plate of Examples 57 and 58 was measured with a scanning electron microscope (SEM). As a result, the film thickness of Example 57 was estimated to be 215 nm, and the film thickness of Example 58 was estimated to be 321 nm. Further, when the surface resistance values of these films were measured by the four-probe method, the film of Example 57 showed conductivity of 4920 Ω / □, and the film of Example 58 showed conductivity of 5290 Ω / □. Furthermore, when the visible light transmittance of the films of Examples 57 and 58 was measured with a spectrophotometer, they showed high transparency of 97.5% and 96.2%.

<Example 59>
First, the particle dispersion of Example 52 (a dispersion in which Ag particles having a concentration of about 30% by weight are dispersed) is diluted with isopropanol so that the content of Ag particles is 20% by weight. A particle dispersion was prepared by dissolving 0.5% by weight of a photoinitiator (Irgacure 500 manufactured by Ciba Specialty Chemicals). Next, the diluted soda glass plate (length 100 mm, width 100 mm, thickness 2.8 mm) is kept at 40 ° C., and this diluted and prepared particle is rotated with a spin coater at a speed of 150 rpm. 5 cc of the dispersion was dropped and shaken for 120 seconds to prepare a film.
A stainless steel photomask was placed on each glass plate with the membrane facing upward. This photomask is formed in a square shape having a length × width × thickness of 100 mm × 100 mm × 1.0 mm, respectively, and three rectangular window holes each having a width × length of 20 mm × 50 mm are formed at intervals of 10 mm. . Next, after irradiating UV energy of 250 mJ / cm ² from above the glass plate with an ultraviolet irradiation device (160 W metal halide lamp: distance 10 cm), the glass plate from which the photomask has been removed is placed on a hot plate and brought to 100 ° C. in the atmosphere. Hold for 10 minutes. Next, the glass plate is rinsed with an ethanol solution in which 10% by weight of N, N-dimethylformamide and 5% by weight of acetylacetone are mixed to dissolve the film of the non-light-irradiated portion, leaving only the light-irradiated film. A patterned film having the same shape as the rectangular window hole of the photomask was obtained. Further, this glass plate was kept at 200 ° C. for 30 minutes in the atmosphere to fire the film, and then cooled to room temperature. This glass plate was referred to as Example 59.
<Example 60>
A glass plate was produced in the same manner as in Example 59 except that the particle dispersion of Example 53 (dispersion in which Ag particles and Pd particles having a concentration of about 30% by weight were dispersed) was used. This glass plate was referred to as Example 60.

<Example 61>
First, the particle dispersion of Example 54 (dispersion in which In particles and Sn particles having a concentration of about 30% by weight were dispersed) was diluted with hexane so that the content of In particles and Sn particles was 1.0% by weight. Then, 0.05 wt% of a photoinitiator (Irgacure 500 manufactured by Ciba Specialty Chemicals) was dissolved in the diluted particle dispersion to prepare a particle dispersion. Next, the cleaned acrylic plate (100 mm long, 100 mm wide, 2.8 mm thick) is kept at 40 ° C. and the acrylic dispersion is rotated at a speed of 150 rpm with a spin coater, and the diluted particle dispersion prepared above. 5 cc was dropped and shaken for 120 seconds to prepare a film.
A stainless steel photomask was placed on each acrylic plate facing the film. This photomask is formed in a square shape having a length × width × thickness of 100 mm × 100 mm × 1.0 mm, respectively, and three rectangular window holes each having a width × length of 20 mm × 50 mm are formed at intervals of 10 mm. . Next, after irradiating ultraviolet energy of 250 mJ / cm ² from above the acrylic plate with an ultraviolet irradiation device (160 W metal halide lamp: distance 10 cm), the acrylic plate with the photomask removed is placed on a hot plate and heated to 100 ° C. in the atmosphere. Hold for 10 minutes. Next, by rinsing the acrylic plate with an ethanol solution in which 10% by weight of N, N-dimethylformamide and 5% by weight of acetylacetone are mixed together, the non-light-irradiated part film is dissolved, leaving only the light-irradiated film. A patterned film having the same shape as the rectangular window hole of the photomask was obtained. Further, the acrylic plate was held at 200 ° C. for 30 minutes in a nitrogen gas atmosphere, and held at 200 ° C. for 60 minutes in the air, and the film was baked and then cooled to room temperature . The children of the acrylic plate was as in Example 61.

<Example 62>
First, the particle dispersion of Example 55 (dispersion in which Au particles having a concentration of about 30% by weight were dispersed) was diluted with hexane so that the content of Au particles was 20% by weight. A particle dispersion was prepared by dissolving 0.5% by weight of a photoinitiator (Irgacure 500 manufactured by Ciba Specialty Chemicals). Next, the diluted soda glass plate (length 100 mm, width 100 mm, thickness 2.8 mm) is kept at 40 ° C., and this diluted and prepared particle is rotated with a spin coater at a speed of 150 rpm. 5 cc of the dispersion was dropped and shaken for 120 seconds to prepare a film.
A stainless steel photomask was placed on each glass plate with the membrane facing upward. This photomask is formed in a square shape having a length × width × thickness of 100 mm × 100 mm × 1.0 mm, respectively, and three rectangular window holes each having a width × length of 20 mm × 50 mm are formed at intervals of 10 mm. . Next, after irradiating UV energy of 250 mJ / cm ² from above the glass plate with an ultraviolet irradiation device (160 W metal halide lamp: distance 10 cm), the glass plate from which the photomask has been removed is placed on a hot plate and brought to 100 ° C. in the atmosphere. Hold for 10 minutes. Next, the glass plate is rinsed with an ethanol solution in which 10% by weight of N, N-dimethylformamide and 5% by weight of acetylacetone are mixed to dissolve the film of the non-light-irradiated portion, leaving only the light-irradiated film. A patterned film having the same shape as the rectangular window hole of the photomask was obtained. Further, this glass plate was kept at 150 ° C. in the air for 30 minutes to fire the film, and then cooled to room temperature. This glass plate was referred to as Example 62.

<Example 63>
First, the particle dispersion of Example 56 (dispersion in which Pt particles having a concentration of about 30% by weight were dispersed) was diluted with propylene glycol monomethyl ether acetate so that the content of Pt particles was 20% by weight. A particle dispersion was prepared by dissolving 0.5 wt% of a photoinitiator (Irgacure 500 manufactured by Ciba Specialty Chemicals) into the particle dispersion. Next, the diluted soda glass plate (length 100 mm, width 100 mm, thickness 2.8 mm) is kept at 40 ° C., and this diluted and prepared particle is rotated with a spin coater at a speed of 150 rpm. 5 cc of the dispersion was dropped and shaken for 120 seconds to prepare a film.
A stainless steel photomask was placed on each glass plate with the membrane facing upward. This photomask is formed in a square shape having a length × width × thickness of 100 mm × 100 mm × 1.0 mm, respectively, and three rectangular window holes each having a width × length of 20 mm × 50 mm are formed at intervals of 10 mm. . Next, after irradiating UV energy of 250 mJ / cm ² from above the glass plate with an ultraviolet irradiation device (160 W metal halide lamp: distance 10 cm), the glass plate from which the photomask has been removed is placed on a hot plate and brought to 100 ° C. in the atmosphere. Hold for 10 minutes. Next, the glass plate is rinsed with an ethanol solution in which 10% by weight of N, N-dimethylformamide and 5% by weight of acetylacetone are mixed to dissolve the film of the non-light-irradiated portion, leaving only the light-irradiated film. A patterned film having the same shape as the rectangular window hole of the photomask was obtained. Further, this glass plate was kept at 150 ° C. in the air for 30 minutes to fire the film, and then cooled to room temperature. This glass plate was referred to as Example 63.

<Comparative test 6 and evaluation>
The thickness, visible light transmittance, and volume resistivity of the glass plate films of Examples 59, 60, 62, and 63 and the acrylic plate film of Example 61 were measured. The thickness of the film was measured with a scanning electron microscope (SEM), the visible light transmittance of the transparent film was measured with a spectrophotometer, and the volume resistivity was measured with a four-probe method. The results are shown in Table 7. In Table 7, “IPA” is an abbreviation for isopropanol, “Hx” is an abbreviation for hexane, and “PGMEA” is an abbreviation for propylene glycol monomethyl ether acetate.

表７から明らかなように、実施例５９、６０、６２及び６３の膜では電極の配線として極めて有効な導電性が得られることが判った。また実施例６１の膜では透明導電膜として極めて優れた可視光透過率と導電性を有することが判った。

As is apparent from Table 7, it was found that the films of Examples 59, 60, 62 and 63 can obtain extremely effective conductivity as electrode wiring. Further, it was found that the film of Example 61 had extremely excellent visible light transmittance and conductivity as a transparent conductive film.

12 Mixture 14 Particle dispersion

Claims (12)

A microwave having an output of 800 to 1250 W in an inert gas atmosphere, a reducing gas atmosphere or an air atmosphere to one or two or more single substances or mixtures selected from the group consisting of organic metal compounds and organic metalloid compounds A method for producing a particle dispersion comprising a step of producing a colloidal particle dispersion that maintains a colloid-specific ink state by irradiating 3 to 10 minutes to disperse the particles and do not precipitate for more than 2 weeks.   The metal contained in the organometallic compound in the group consisting of the organometallic compound and the organometalloid compound is Cu, Au, Ag, Pt, Pd, Ru, Rh, Re, Os, Ir, Sc, Y, Ti, Zr. , V, Nb, Ta, Cr, Mo, W, Mn, Fe, Co, Ni, Zn, Cd, Al, Ga, In, Tl, Sn, Pb, La, Ce, Nd, Sm, Eu, Gd, Tb The method for producing a particle dispersion according to claim 1, wherein the metal dispersion is one or more metals selected from the group consisting of Er, Tm, and Yb.   The metalloid contained in the organic metalloid compound in the group consisting of the organic metal compound and the organic metalloid compound is one or more metalloids selected from the group consisting of Si, Ge, Sb and Bi. A method for producing the particle dispersion according to claim 1.   The method for producing a particle dispersion according to claim 1, wherein the organic component of the organic metal compound or organic metalloid compound is one or more compounds selected from the group consisting of organic acids and amines. The method for producing a particle dispersion according to claim 4 , wherein the organic acid is one or more compounds selected from the group consisting of compounds containing carbon having 2 to 29 carbon atoms. Organic acids are malic acid, citric acid, fumaric acid, maleic acid, tartaric acid, acetic acid, propionic acid, butyric acid, isobutyric acid, vibalic acid, valeric acid, isovaleric acid, caproic acid, 2-ethylbutyric acid, caprylic acid, pelargon Acid, 2-ethylhexanoic acid, capric acid, undecanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, arachidic acid, behenic acid, lignoceric acid, serotic acid, montanic acid, melicic acid, ricinoleic acid, The particle according to claim 4, which is one or more organic acids selected from the group consisting of 12-hydroxystearic acid, naphthenic acid, abietic acid, dextropimaric acid, palmitoleic acid, oleic acid, linoleic acid and linolenic acid. A method for producing a dispersion. In a colloidal particle dispersion, tin oxide, indium oxide, zinc oxide, tin-containing indium oxide (ITO), zinc-containing indium oxide (IZO), aluminum-containing zinc oxide (AZO) having an average particle size of 0.005 to 1.0 μm ), Gallium-containing zinc oxide (GZO), cerium-containing zinc oxide (CZO), boron-containing zinc oxide (BZO), antimony-containing tin oxide (ATO), or phosphorus-containing tin oxide (PTO). Item 7. A method for producing the particle dispersion according to any one of Items 1 to 6 . From Cu, Au, Ag, Pt, Pd, Ru, Rh, Re, Fe, Co, Ni, Zn, In, Sn, and Sb having an average particle size of 0.005 to 1.0 μm in a colloidal particle dispersion. one or more pure metal particles selected from the group consisting claim 1 comprising mixed metal particles or alloy particles, 2 or 4 the method to produce particles dispersion according to any one. The method for producing a particle dispersion according to any one of claims 1 and 3, wherein the colloidal particle dispersion contains Sb semimetal particles having an average particle diameter of 0.005 to 1.0 µm. The particle dispersion obtained by the method according to claim 7 is dried, and tin oxide, indium oxide, zinc oxide, tin-containing indium oxide (ITO) having an average particle diameter of 0.005 to 1.0 μm, zinc-containing oxidation Indium (IZO), aluminum-containing zinc oxide (AZO), gallium-containing zinc oxide (GZO), cerium-containing zinc oxide (CZO), boron-containing zinc oxide (BZO), antimony-containing tin oxide (ATO), or phosphorus-containing tin oxide The manufacturing method of the oxide semiconductor particle including the process of manufacturing the oxide semiconductor particle of (PTO). The particle dispersion obtained by the method according to claim 8 is dried to obtain Cu, Au, Ag, Pt, Pd, Ru, Rh, Re, Fe, Co having an average particle diameter of 0.005 to 1.0 μm. , Ni, Zn, In, Sn, and a method for producing metal particles, including a step of producing metal particles made of two or more kinds of pure metals, mixed metals or alloys selected from the group consisting of Sb and Sb. A method for producing semimetal particles, comprising drying the particle dispersion obtained by the method according to claim 9 to produce Sb semimetal particles having an average particle diameter of 0.005 to 1.0 µm.

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