583288 A7 修 __B7 ___ -五、發明說明（/ ) 技術領域 (請先閱讀背面之注意事項再填寫本頁) 本發明係有關於一種製備高濃縮金屬膠體溶液之方法 ' ，一種得自於該方法之高濃縮金屬膠體溶液，及一種經由 使用該高濃縮金屬膠體溶液而得到之塗層。 前案技藝 所謂的金屬膠體溶液，即直徑度量爲數十奈米的金屬 粒子於溶液中之均勻分散液，已經利用其獨特性質而應用 於各種不同的領域中。日本公開公告平(Hei)-ll-080647揭示 貴重金屬的膠體粒子，含高分子量顏料分散劑的貴重金屬 膠體粒子及製備它們的方法，其亦教示可將它們應用在塗 料及相似者中做爲色料。日本公開公告2000-239853揭示 上述的貴重金屬膠體粒子於製備具有金凰光澤的薄膜的用 途。關於此點，爲了形成具有極佳金屬外觀的薄膜，金屬 含量較佳爲儘可能地高。 另一方面，電導性塗料已經使用在各種不同電子裝置 、電子元件和電子電路中作爲電容器和片形電阻器之電極 材料，載於陶瓷基質上之導體電路等等。通常此種電導性 塗料係藉由施用含金屬粒子的電導性糊狀物而形成。在這 情況下，由電導性觀點而言，金屬含量亦較佳爲儘可能地 咼。 然而，如果在製造含有局子量顏料分散劑的貴重金屬 膠體粒子時，由於金屬濃度的增加而使所使用的高分子量 顏料分散劑數量降低時，則在還原階段無法確保足夠的分 散液穩定性。 3 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） " 一 583288 - __一11 —583288 A7 修 __B7 ___ -V. Description of the invention (/) Technical field (please read the notes on the back before filling this page) The present invention relates to a method for preparing highly concentrated metal colloidal solutions', one obtained from the Method for highly concentrated metal colloid solution, and a coating obtained by using the highly concentrated metal colloid solution. The technique of the previous case The so-called metal colloid solution, that is, the uniform dispersion of metal particles in solution with a diameter of tens of nanometers, has been used in various fields by utilizing its unique properties. Japanese Laid-Open Publication (Hei) -ll-080647 discloses colloidal particles of precious metals, precious metal colloidal particles containing a high molecular weight pigment dispersant, and a method for preparing them. It also teaches that they can be applied to coatings and the like as Colorants. Japanese Laid-Open Publication No. 2000-239853 discloses the use of the above-mentioned precious metal colloidal particles for the production of a thin film having a golden phoenix gloss. In this regard, in order to form a film having an excellent metallic appearance, the metal content is preferably as high as possible. On the other hand, conductive coatings have been used as electrode materials for capacitors and chip resistors in various electronic devices, electronic components and electronic circuits, conductor circuits on ceramic substrates, and so on. Such conductive coatings are generally formed by applying a conductive paste containing metal particles. In this case, from the viewpoint of conductivity, the metal content is also preferably as high as possible. However, when the precious metal colloidal particles containing a local pigment dispersant are produced, the amount of the high molecular weight pigment dispersant used is reduced due to an increase in the metal concentration, and sufficient dispersion stability cannot be ensured at the reduction stage. . 3 This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) " a 583288-__ 一 11 —
A7 B7 一 ^ ~ 五、發明說明（2 ) 本發明槪述 Γ%先閱讀背面之沒意亊項再填寫本頁) 本發明的一個標的爲提供一種製造方法，其即使載爲 了確保分散液穩定性而使用大量高分子量顏料分散劑時， 仍可得到顯示高金屬濃度的高濃縮金屬膠體溶液。 本發明係有關於一種製備高濃縮金屬膠體溶液之方法 ，其包括從含有金屬膠體粒子和該高分子量顏料分散劑的 溶液中部份移除高分子量顏料分散劑。該高分子量顏料分 散劑的部份移除較佳係利用離心進行，且更佳的是，該離 心係在不低於1000 G下進行。此外，高分子量顏料分散劑 的部份移除較佳係利用超濾進行，且更佳的是，該超濾之 進行係使用具有截留（cutoff)分子量3000至80000的過 濾膜。 上述含有金屬膠體粒子和高分子量顏料分散劑的溶液 較佳係經由在高分子量顏料分散劑存在下還原金屬化合物 而得到。含有金屬膠體粒子和高分子量顏料分散劑的溶液 中固態物質的金屬濃度較佳係不高於85質量％，且高濃縮 金屬膠體溶液中固態物質的金屬濃度較佳係不低於90質量 %。 高濃縮金屬膠體溶液與含金屬膠體粒子和高分子量顏 料分散劑的溶液之間，固態物質之金屬濃度的差異較佳係 不低於10質量％。 本發明亦有關於一種得自於上述方法的高濃縮金屬膠 體溶液。 本發明進一步係有關於一種經由使用該高濃縮金屬膠 4 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 583288 _ A7 --------- R7_ -五、發明說明〇 ) 體溶液而得到的塗層。 本發明詳細敘述 現在將進一步詳細敘述本發明。 —種製備本發明高濃縮金屬膠體溶液之方法包括從含 有金屬膠體粒子和高分子量顏料分散劑的溶液中部份移除 高分子量顏料分散劑，藉此增高其固態物質的金屬濃度。 上述含有金屬膠體粒子和高分子量顏料分散劑的溶液 可藉由在高分子量顏料分散劑存在下還原金屬化合物得到 Ο 上文中所提及的金屬化合物是一種當溶解於溶劑時可 釋出金屬離子且在還原該金屬離子時可提供金屬膠體粒子 的化合物。可轉變成該金屬膠體粒子的金屬並不特別地限 制’但爲了提供良好的電導性塗料或具有極佳金屬外觀的 塗層，較佳係使用貴重金屬或銅。於上文中所提及之貴重 金屬並不特別地限制，但包括金，銀，釕，铑，鈀，餓， 銥，鉑等等。於其中較佳者爲金，銀，鉑和鈀。 上文中所提及的金屬化合物並不特別地限制但需含有 該等金屬的任何一種，因此例如包括氫四氯金酸（皿）· 4H2〇（氯金酸），硝酸銀，乙酸銀，過氯酸銀(IV)，氫六氯 鉑酸（IV) · 6出0 (氯鈾酸），氯鉑酸鉀，氯化銅（π) · 2H2〇 ，乙酸銅（Π) · 1H2〇，硫酸銅（Π)，氯化鈀（Π) · 2H2〇及三 氯化铑（瓜）· 3出0。它們可單獨使用或將二種或以上物種 合倂使用。 上述金屬化合物的使用比率較佳爲其在溶劑中的金屬 5 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 」——、--------pi — (請先閱讀背面之注意事項再填寫本頁) Γ訂· -1線- 583288 A7 ' _B7___ 。五、發明說明（f ) 莫耳濃度不低於0·01莫耳/升。如果濃度低於〇.01莫耳/升 ，則在所得到金屬膠體溶液中的金屬莫耳濃度將會過低而 無法提供有效的操作。較佳爲不低於0.05莫耳/升，更佳爲 不低於0.1莫耳/升。 上文中所述及的溶劑並不特別地限制，但其需能夠溶 解該金屬化合物，因此包括例如水，有機溶劑和相似者。 上述有機溶劑並不特別地限制但包括例如具有1至4個碳 原子的醇類，如乙醇、乙二醇等；酮類，如丙酮；及酯類 ，如乙酸乙酯及諸如此類。這些溶劑可單獨使用或將二種 或以上物種合倂使用。當上述溶劑爲水和有機溶劑的混合 物時，其中的有機溶劑較佳爲水溶性者，例如丙酮，甲醇 ，乙醇，乙二醇及諸如此類。在本發明的施行中，較佳係 使用水、醇或水-醇的混合溶液，因此這類溶劑適用於在接 下來階段中利用超濾將高分子量顏料分散劑部分移除的方 法。 上文中所提及的高分子量顏料分散劑不僅是一種納入 對顏料表面具有高親和力之官能基的高分子量聚合物，其 亦是一種含有包含具有溶劑化部位之結構的兩親性共聚物 ，其通常在顏料糊狀物的製造方法中用作顏料分散劑。 上文中所提及的高分子量顏料分散劑被認爲是與該金 屬膠體粒子共存，且可使金屬膠體粒子在溶劑中的分散液 穩定化。 該高分子量顏料分散劑的數目平均分子量較佳爲1000 至1000000。如果低於1000，則可能無法得到充份的分散 6 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） (請先閱讀背面之注意事項再填寫本頁) • _ --線- 583288 A7 '____ B7___ -五、發明說明（5 ) 液穩定性。如果高於1000000，其則黏度傾向於變得過高而 無法確保良好的處理。數目平均分子量更佳爲2000至 500000，且再更佳爲4000至500000。 高分子量顏料分散劑並不特別地限制，但其需具有上 文中所提及之性質，例如包括於日本公開公告平-11-80647 中所揭示之化合物。 可以利用市售產品以及各種不同的化合物做爲高分子 量顏料分散劑。在那些市售產品之中，可提及者例如爲 Solsperse 20000，Solsperse 24000，Solsperse 26000， Solsperse 27000，Solsperse 28000，Solsperse 41090 (全爲 AVECIA 公司的產品）；Disperbyk-160，Disperbyk-161， Disperbyk-162，Disperbyk-163，Disperbyk-166，Disperbyk-170，Disperbyk-180，Disperbyk-181 ，Disperbyk-182， Disperbyk-183 » Disperbyk-184 5 Disperbyk-190 5 Disperbyk-191 ，Disperbyk-192，Disperbyk-2000，Disperbyk-2001 (全爲 BYK-Chemie 的產品），Polymer 100，Polymer 120，Polymer 150，Polymer 400，Polymer 401，Polymer 402，Polymer 403 ，Polymer 450，Polymer 451，Polymer 452，Polymer 453， EFKA-46，EFKA-47，EFKA-48，EFKA-49，EFKA-1501， EFKA-1502，EFKA-4540，EFKA-4550 (全爲 EFKA 化學品 公司的產口口口）； FLCJWLEN DOPA-158，FLOWLEN DOPA-22 ^ FLOWLEN DOPA-17 ^ FLOWLEN G-700 ^ FLOWLEN TG-720W，FLOWLEN-730W，FLOWLEN-740W，FLOWLEN-745W (全爲Kyoeisha化學品公司的產品）；Ajisper PA111 7 本紙張尺度適用中國國家標準（CNS)A4規格（210 x 297公釐） 」——.--------#丨| (請先閱讀背面之注意事項再填寫本頁) . ί線· 583288 A7 -___B7___ -五、發明說明（6 ) ，Ajisper PB711，Ajisper PB811，Ajisper PB821，Ajisper FW911 (全爲 Ajinomoto 公司的產品）；及 Joncryl 678， Joncryl 679，Joncryl 62 (全爲Johnson聚合物公司的產品） 。它們可單獨使用或將二種或以上物種合倂使用。 該高分子量顏料分散劑的用量，相對於該金屬化合物 中之金屬和高分子量顏料分散劑的合倂量而言較佳爲不低 於15質量％。如果低於15質量％，則在還原階段中無法 具有足夠的分散液穩定性，且對增加金屬濃度的成果會降 低。其中並無特別的上限，但是例如可將該金屬化合物中 之金屬質量的10倍視爲上限。 上述的金屬化合物可藉由在該高分子量顏料分散劑存 在下使還原化合物與之反應而還原成金屬。上述之還原化 合物較佳爲胺。當將胺加至含有該金屬化合物和高分子量 顏料分散劑的溶液內且該將溶液攪拌/混合時，金屬離子係 在室溫左右還原成金屬。藉由使用該胺時，金屬化合物可 在約5至100°C且較佳爲約20至80°C之溫度被還原，而無 需使用極危險或有毒的還原劑、加熱儀器或特別的輻射設 備。 於上文中所提及之胺並未特別地限制，但是可使用例 如於日本公開公告平_11-80647中所提及的化合物。因此， 可提及者有脂肪族胺類，例如丙胺，丁胺，己胺，二乙基 胺，二丙基胺，二甲基乙胺，二乙基甲胺，三乙基胺，乙 二胺，N，N，N、N'-四甲基亞乙基二胺，l，3-二胺基丙烷， Ν,Ν,Ν'Ν'-四甲基-1,3-二胺基丙烷，三亞乙基四胺，四亞 8 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） I---.--------i — (請先閱讀背面之注意事項再填寫本頁) 訂， --線· 583288 A7 ' _ — _B7___ ，五、發明說明（7) ---------------- (請先閱讀背面之注意事項再填寫本頁) 乙基五胺寺；脂環族胺類’例如呢卩定，N-甲基顿陡，派啡 ，N，N'-二甲基顿啡，吡咯烷，N-甲基吡咯烷，嗎咐等；芳 香族胺類，例如苯胺，N-甲基苯胺，n，N-二甲基苯胺，甲 苯胺，甲氧基苯胺，乙氧基苯胺等；及芳烷基胺類，例如 苯甲基胺，N-甲基苯甲基胺，N，N-二甲基苯甲基胺，苯乙 基胺，苯二甲胺，N，N，N'，N'-四甲基苯二甲胺及諸如此類 。就上述胺的進一步例子而言，舉例言之，可提及者有院 醇胺類，例如甲基胺基乙醇，二甲基胺基乙醇，三乙醇胺 ，乙醇胺，二乙醇胺，甲基二乙醇胺，丙醇胺，2-(3-胺基 丙基胺基）乙醇，丁醇胺，己醇胺，二甲基胺基丙醇及諸如 此類。其中，鏈烷醇胺類爲較佳者，且二甲基胺基乙醇爲 最佳者。 線. 除了胺類，亦可使用鹼金屬硼氫化物，例如用作習用 還原劑的硼氫化鈉；聯胺化合物；檸檬酸；酒石酸；抗壞 血酸；甲酸；甲醒；二亞硝基硫鹽(dinithionites)，次硫酸 鹽衍生物等。由適用性觀點而言，較佳爲檸檬酸，酒石酸 或抗壞血酸。它們可單獨地使用，或與該胺倂用，且當胺 與檸檬酸、酒石酸、或抗壞血酸倂用時，檸檬酸、酒石酸 或抗壞血酸較佳係以各別的鹽形式使用。當檸檬酸或次硫 酸鹽衍生物與鐵（Π)倂用時可改良還原反應的效率。 該還原化合物的添加量較佳爲不低於可還原存在於金 屬化合物之金屬的所需數量。如果低於此數量，還原反應 的進行傾向於不夠完全。其中的上限並不特別地限制，但 較佳爲不大於可還原存在於金屬化合物之金屬所需數量的 9 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 583288 A7 ' ___B7____ -五、發明說明（？） 30倍，更佳爲不大於1〇倍。 ---------------- (請先閱讀背面之注意事項再填寫本頁) 除了包含加入該種還原化合物的化學還原反應，亦可 同樣地使用以高壓汞蒸氣燈的輻照技術。 該還原化合物的加入程序並不特別地限制，但舉例言 之，該還原化合物可在加入高分子量顏料分散劑之後加入 。在此種情況下，進行還原反應的方法包含事先在溶劑中 溶解該高分子量顏料分散劑，於其中加入該還原化合物和 金屬化合物，及於混合物中加入其餘者，亦即在上述步驟 中並未使用的還原化合物或金屬化合物。加入該還原化合 物的步驟包含事先混合高分子量顏料分散劑和還原化合物 ，及將所得到之混合物加至含有金屬化合物的溶液中。 上述之還原作用得到含有平均粒徑約5至100奈米的 金屬膠體粒子的溶液。 在該還原反應之後所得到的溶液是一種含有金屬膠體 粒子和高分子量顏料分散劑的膠體溶液。於本文中所使用 的『膠體溶液』一詞意指金屬微細粒子係分散於溶劑中， 因此分散液可由目視地認定爲溶液。 在該還原反應之後所得到的溶液不僅含有金屬膠體粒 子和高分子量顏料分散劑，同時含有其他的雜質離子，例 如衍生自金屬膠體溶液原料的氯離子，得自於還原反應的 鹽及依各案例而定的胺。由於這些雜質離子，鹽和胺對於 所得金屬膠體溶液的穩定性具有不利影響，因此最好是將 其等移除。這些成份的移除可以利用電透析，離心，超濾 或相似者，但是離心和超濾是較佳的技術，因爲這些技術 10 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 583288 A7 * ________Β7__ —-~- - --------- -五、發明說明（？） 可同時增加金屬的濃度，如將於下文中說明者。 Γ 清先閱讀背面之注意事項再填寫本頁) 再而，於製備本發明高濃縮金屬膠體溶液的方法中， 金屬濃度係藉由部份移除高分子量顏料分散劑而增加。$ 來以作爲高分子量顏料分散劑部份移除的基質的金屬膠胃 溶液較佳爲一種溶液且其中包含於金屬膠體粒子和高分子 量顏料分散劑中的固體物質爲溶液總質量的0.05至50%。 如果低於0.05%，則金屬莫耳濃度將會過低而無法提供有 效率的操作。如果超過50%，則不易進行高分子量顔料分 散劑的部份移除。而且，該固體物質的金屬濃度較佳爲不 高於85質量％。 高分子量顏料分散劑的部份移除可利用離心或超濾有 效地進行。 •線· 在離心方法中，金屬膠體粒子沈殿出，但無需的雜質 離子，鹽和胺以及高分子量顏料分散劑仍溶解於上淸液中 。因此，這些成份可藉由上淸液的倒棄而移除。剩下的金 屬膠體粒子可使用加入溶劑來淸洗，且一次又一次地離心 來提高移除效果。 離心較佳係於不低於1000 G下進行。如果是在低於 1000 G之下進行，則不易進行高分子量顏料分散劑的部份 移除。離心的條件依據金屬膠體的粒子直徑而定，例如直 徑爲奈米級次的粒子欲進行沈澱時，便需使用所謂超離心 的條件。標準條件可爲在3000 G下進行5至60分鐘，較 佳爲15至45分鐘。 上述的離心方法可藉由改變上述的重力加速度速率、 11 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公爱） A7 583288 ___B7___ 五、發明說明（/ 0 ) 滯留性，及/或操作次數’依據粒子直徑而將金屬膠體粒子 分級。藉著此種分級，可以得到具有適用於不同用途的各 種不同粒子直徑的高濃縮金屬膠體粒子溶液，而且同時可 將金屬膠體粒子的直徑調整至某種程度。 由上述離心方法所得到的高濃縮金屬膠體溶液具有極 高的濃度，致使其常爲糊狀物形式。較佳的濃度通常爲不 低於80質量％的固體。其中的上限並不特別地限制，但是 當考慮運送的簡易性時則爲不高於90質量％。 超濾可使用於進行高分子量顏料分散劑的部份移除。 超濾（UF)所使用的濾膜相較於在微濾（MF)中使用者， 其係爲更微細網目的膜。超濾的進行通常是爲了分離高分 子量物質和膠質物質，其使用於本發明的目的是爲了增加 金屬膠體溶液中固體物質的金屬濃度。 通常具有粒子直徑爲1奈米至5微米的物質可利用上 述的超濾分離出。藉由使用上述的粒子直徑做爲截留點， 不僅可移除不必要的雜質離子，鹽和胺亦可移除高分子量 顏料分散劑，因此增加金屬膠體溶液中固體物質的金屬濃 度。如果截留點低於1奈米，不想要的成份將不會通過濾 膜’因此無法移除。如果高於5微米，則許多金屬膠體粒 子可容易地通過濾膜使得無法得到所欲的高濃縮金屬膠體 溶液。 用於該超濾的濾膜並不受到特別地限制，但是通常係 使用由樹脂材料所製得的膜，例如聚丙烯腈，氯乙烯-丙稀 腈共聚物，聚硼，聚醯亞胺，聚醯胺或相似者。在這些樹 ___ 12 本紙張尺度適用中國國家標準（CNS)A4規格（21〇 x 297公釐） (請先閱讀背面之注音？事項再填寫本頁) 訂-· 583288 A7 ___B7__ -五、發明說明（"） 脂材料中，較佳者爲聚丙烯腈或聚碾’且更佳者爲聚丙烯 腈。爲了在超濾之後通常需進行的濾膜淸洗可有效率地執 行，較佳爲使用容許反淸洗的濾膜於超濾。 使用於超濾的較佳濾膜需可截留3000至80000的分子 量。如果低於3000，則無法充份地移除不想要的高分子量 顏料分散劑和其他物質。如果高於80000 ’則金屬膠體粒 子可容易地通過濾膜而無法得到所欲的金屬膠體溶液。其 中更佳之範圍爲10000至60000。『截留分子量』通常意謂 當聚合物溶液穿經超濾膜時經由超濾膜孔隙被排除的聚合 物分子的分子量，且係用作濾膜孔隙直徑的準則。截留分 子量愈高，濾膜的孔隙直徑愈大。 該超濾的濾膜單元幾何形狀並不特別地限制，但依據 濾膜的幾何形狀而定，可包括中空片單元（亦稱之爲毛細 管單元），螺旋單元，管狀單元，板單元等等，且其中之任 何一種均可有利地使用於本發明操作。由於膜面積愈大愈 可簡易地縮減過濾時間，所以由效率的觀點而言較佳爲使 用可簡易過濾的中空片單元。更甚者，如果欲處理的金屬 膠體溶液數量極大時，較佳爲使用包含大量超濾膜單位的 單元。 所使用的超濾方法並不特別地限制，但可包括例如習 知的方法。通常，依據上述反應所得到之含有金屬膠體粒 子和高分子量顏料分散劑的溶液通經超濾膜，藉此移除含 有雜質離子，鹽’胺和高分子量顏料分散劑的濾液。此種 超濾通常會重複至濾液中的雜質離子濃度降低至所需水平 _ __ 13 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公爱） ---------------- (請先閱讀背面之注意事項再填寫本頁) 、—訂i 線- 583288 A7 -____B7 __ _五、發明說明（A) 。在進行此種操作時，較佳係加入與被移除濾液等量的溶 劑，藉此調節欲處理之金屬膠體溶液的濃度至固定的水平 。藉由使用與還原階段所使用溶劑不同的溶劑，在金屬膠 體溶液中會產生溶劑交換。 上文中所提及之超濾可使用習知的方式實行’例如批 次方式。批次超濾的方法包含在超濾進行時加入欲處理的 金屬膠體溶液。當雜質離子進行移除至所需的濃度水平之 後，可進一步進行超濾使固體含量增加。 可藉由離心及/或超濾而得到的高濃縮金屬膠體溶液 ，相較於處理之前之含有金屬膠體粒子和高分子量顏料分 散劑的溶液，其固體物質的金屬濃度已然提高，但特定金 屬濃度數値則依溶液在處理之前的金屬濃度而定。較佳％ ，在處理之前，金屬膠體粒子和高分子量顏料分散劑溶液 中所含固體物質的金屬濃度爲不高於85質量％，但在處ί里 之後，高濃縮金屬膠體溶液中固體物質的金屬濃度爲不低 於90質量％。在處理之前的溶液與處理之後的溶液之間， 金屬濃度的較佳差異爲低於10質量％。 利用離心所得到的高濃縮金屬膠體溶液，其固體含裊 相較於利用超濾所得到溶液中含有者爲更高，但兩種情況 均較佳爲藉由加入溶劑使最終的固體含量調整爲1至50胃 量％。再次地，當使用與還原階段所使用溶劑不同的溶劑 時，在金屬膠體溶液中會產生溶劑交換。 因此得到的高濃縮金屬膠體溶液在固體物質中具有較 高之金屬濃度，因此其可充份地顯示出金屬的固有性質， I ——*--------pi- (請先閱讀背面之注意事項再填寫本頁) 訂· -線· 14 583288 A7 '_ B7 _ ，五、發明說明（Ο ) 例如高電導性，金屬光澤，染色能力，熱傳導性及諸如此 類。此外，因爲在金屬膠體溶液中的高分子量顏料分散劑 濃度已降至低水平，此種溶液適用於塗覆基質而在其上形 成金屬塗層。該基質的塗覆方法並未特別地限制，但是例 如包括各種不同習知方法。 於上文中所提及之金屬塗層可爲具有金屬光澤之電導 性塗覆物或塗層。 上述的金屬膠體溶液亦可在樹脂模製品，例如光學材 料或塗料組成物，中做爲色料，亦可使用於此類領域中做 爲抗微生物物質，催化劑，化妝品，電磁遮蔽物及諸如此 類。 依據本發明的製備方法，即使爲了確保分散液穩定性 而使用大量高分子量顏料分散劑時，仍可得到顯示高金屬 濃度的高濃縮金屬膠體溶液。所得到的高濃縮金屬膠體溶 液可非常有利地用於形成具有電導性及/或金屬光澤的金屬 塗層。 施行本發明的最佳模式 下列實施例將更詳盡地說明本發明，但這些實施例絕 非本發明範圍之限制。在實施例中，％係指質量％。 實施例1 在一個2升燒瓶內加入6.2克Disperbyk-191 (BYK-Chemie的產品）和280.2克乙醇。將燒瓶固定於水浴中且 在50°C下攪拌內容物至Disperbyk-191完全溶解。於固定攪 拌下於溶液中加入溶解於280.2克乙醇的30.0克氯金酸， 15 ί紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） - ---------------- (請先閱讀背面之注意事項再填寫本頁) · 線- 583288 A7 ___B7____ 五、發明說明（4) --------------- (請先閱讀背面之注意事項再填寫本頁) 且將混合物在50°C下攪拌10分鐘。然後，加入32.4克二 甲基胺基乙醇，同時之間溶液迅速轉變爲黑色且溶液溫度 昇高至63°C。靜置該溶液，且當溶液溫度降至50°C時’在 相同的溫度下將溶液進一步攪拌2小時以得到黑紫色的黃 金膠體乙醇溶液。 然後，超濾單元AHP1010 (Asahi化學工業公司的產 品；截留分子量50000，400單位膜），磁性泵及於底部裝 置有管連接器的3升不銹鋼杯，係藉矽氧烷管互相連接而 組裝成超濾系統。將上文中所提及之黃金膠體乙醇溶液置 於不銹鋼杯，在加入2升乙醇之後，啓動泵開始進行超濾 。大約40分鐘之後，當由單元中所得到的濾液數量達到2 升時，於不銹鋼杯內補充2升的乙醇。然後，當確定濾液 的電導性爲30//S/cm或更低時，將母液濃縮至500毫升。 -線 然後，使用500毫升不銹鋼杯，超濾單元AHP0013 ( Asahi化學工業公司的產品；截留分子量50000，400單位 膜），管式泵和吸氣器裝配超瀘系統。將上文中所得到的母 液置於不銹鋼杯內並濃縮，使固體含量增加。當母液量變 爲大約100毫升時，停止泵使濃縮完成，藉此得到具有3〇 %固體的黃金膠體乙醇溶液。在溶液中的黃金膠體粒子平 均直徑經由電子顯微鏡檢測爲22奈米。包含黃金膠體粒子 和高分子量顏料分散劑之固體物質中的黃金含量由 DTA (Seiko儀器的產品）測得，相對於在所加入原料中所 含有的70質量％，其爲90質量％。 將3克之上述黃金膠體乙醇溶液部份滴至1〇平方公 16 本紙張尺度適用中國國家標準(CNS)A4規格（21〇 X 297公爱） """"""""-一-— — 583288 A7 • _B7____ -五、發明說明（J) 1--------pi — (請先閱讀背面之注意事項再填寫本頁) 分玻璃板的中央，使用旋轉塗覆技術平均地展開，在第一 個階段係使用旋轉塗覆器以400 rpm進行5秒，且在第二 階段則以600 rpm進行30秒，得到略黑的黃金薄膜。將此 板置於烤爐內，於150°C下乾燥10分鐘使溶劑移除。然後 ，將該板在250°C下燒烤50分鐘而得到0.7微米厚且具有 金屬光澤之金屬塗層。此金屬塗層的表面電阻性經由 Loresta FP (Mitsubishi化學品公司的產品）測量爲〇.〇8Ω/ 實施例2 線- 重複實施例1的步驟，除了將第一次試驗所使用的超 濾單元由AHP1010換成ACP1010 (Asahi化學工業公司的 產品；截留分子量13000，400單位膜），且將第一超濾試 驗所加入的乙醇以等量的去離子水取代，因此得到具有30 %固體的黃金膠體水溶液。在此溶液中的黃金膠體粒子平 均直徑爲21奈米。固體物質中的黃金含量由TG-DTA ( Seiko儀器的產品）測得，相對於在所加入原料中所含有的 70質量％，其爲90質量％。 實施例3 在一個500毫升燒瓶內加入4.9克EFKA 4550 ( EFKA 化學品公司的產品），112.1克乙醇及13.0克二甲基胺基乙 醇。將燒瓶固定於水浴中且將內容物在50°C下攪拌大約1〇 分鐘直至EFKA 4550完全溶解。在持續攪拌下，於溶液中 加入溶解於112.1克乙醇的12.0克氯金酸，同時之間溶液 迅速轉變爲黑色且溶液溫度昇高至58°C。靜置該溶液，且 17 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 583288 A7 參 __ B7______ -五、發明說明（Μ) 當溶液溫度降至50°C時，在相同的溫度下將溶液進一步攪 拌2小時以得到黑紫色的黃金膠體乙醇溶液。 然後，使用500毫升不銹鋼杯，超濾單元AHP0013 ( Asahi化學工業公司的產品；截留分子量50000，100單位 膜），管式泵和吸氣器裝配超瀘系統。將上文中所得到的黃 金膠體乙醇溶液置於不銹鋼杯內並開始超濾的操作。大約 30分鐘之後，由單元中所得到的濾液數量達到300毫升時 ，於不銹鋼杯內補充300毫升的乙醇。然後，當確定濾液 的電導性爲30//S/cm或更低時，將母液濃縮爲50毫升， 因而得到具有25%固體的黃金膠體乙醇溶液。在溶液中的 黃金膠體粒子平均直徑爲24奈米。包含黃金膠體粒子和高 分子量顏料分散劑之固體物質的黃金含量由TG-DTA( Seiko儀器的產品）測得，相對於在所加入原料中所含有的 70質量％，其爲90質量％。 實施例4 在一個500毫升燒瓶內加入4·6克Disperbyk-184 ( BYK-Chemie的產品），112.1克去離子水及13.0克二甲基胺 基乙醇，將其中的內容量於室溫下攪拌約10分鐘。於持續 攪拌下，於溶液中加入溶解於112.1克去離子水的12.0克 氯金酸，同時之間溶液迅速轉變爲黑色且溶液溫度昇高至 20°C至28°C。攪拌進一步持續2小時，藉此得到黑紫色的 黃金膠體水溶液。 然後，使用500毫升不銹鋼杯，超濾單元AHP0013 ( Asahi化學工業公司的產品；截留分子量50000，100單位 18 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） (請先閱讀背面之注意事項再填寫本頁) --線- 583288 A7 ，___B7 _ ，五、發明說明（卩） 膜），管式泵和吸氣器裝配超濾系統。將上文中所得到的黃 金膠體水溶液置於不銹鋼杯內並開始超濾的操作。大約30 分鐘之後，由單兀中所得到的濾液數量達到300毫升時， 於不銹鋼杯內補充300毫升的去離子水。當確定濾液的電 導性爲300// S/cm或更低時，將母液濃縮爲50毫升，因而 得到具有25%固體的黃金膠體水溶液。在溶液中的黃金膠 體粒子平均直徑爲25奈米。包含黃金膠體粒子和高分子量 顏料分散劑之固體物質中的黃金含量由TG-DTA (Seiko儀 器的產品）測得，相對於在所加入原料中所含有的70質量 %，其爲90質量％。 實施例5 在一個2升燒瓶內加入14.0克Disperbyk-190 (BYK· Chemie的產品），294.3克的1莫耳/升硝酸，及294.3克去 離子水。將燒瓶固定於水浴中且將內容物在50°C下攪拌至 Disperbyk-190完全溶解。於固定攪拌下於溶液中加入溶解 於883.0克去離子水的50.0克硝酸銀，且將混合物在70°C 下進一步攪拌10分鐘。然後，加入131.0克二甲基胺基乙 醇，同時之間溶液迅速轉變爲黑色且溶液溫度昇高至76t 。靜置該溶液，且當溶液溫度降至70°C時，在相同的溫度 下將溶液進一步攪拌2小時以得到黑黃色的銀膠體水溶液 。將反應混合物轉移至一個1升的塑膠瓶內且靜置於60°C 的恆溫箱內18小時。然後，超濾單元AHP1010 (Asahi化 學工業公司的產品；截留分子量50000，400單位膜），磁 性泵及於底部裝置有管連接器的3升不銹鋼杯，係藉矽氧 19 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） (請先閱讀背面之注意事項再填寫本頁) 訂· -線- 583288 A7 會_____B7__ •五、發明說明（） 烷管互相連接而組裝成超濾系統。將上文中所提及靜置於 60°C恆溫箱內18小時之反應混合物置於不銹鋼杯，在加入 2升去離子水之後，啓動泵開始進行超濾。大約40分鐘之 後，由單元中所得到的濾液數量達到2升時，於不銹鋼杯 內補充2升的去離子水。然後，當確定濾液的電導性爲 300//S/cm或更低時，將母液濃縮爲500毫升。 然後，使用500毫升不銹鋼杯，超濾單元AHP0013 ( Asahi化學工業公司的產品；截留分子量50000，100單位 膜），管式泵和吸氣器裝配超濾系統。將上文中所得到的母 液置於不銹鋼杯內並濃縮，使固體含量增加。當母液數量 達到大約100毫升時，停止泵使濃縮完成，藉此得到具有 30%固體的銀膠體水溶液。在溶液中的銀膠體粒子平均直 徑爲27奈米。固體物質中的銀含量由TG_DTA (Seik0儀器 的產品）測得’相封於在所加入原料中所含有的8 5晳量％ ，其爲90質量％。 實施例6 重複實施例5的步驟’除了將第〜次試驗所使用的超 濾單元由AHP1010換成ACP1010 (ASahi化學工業公司的 產品；截留分子量13000，400單位膜），且g第一次超爐 試驗所加A的去離子水以等量的乙醇取代，因此得到具有 30%固體的銀膠體乙醇溶液。在此溶液中的銀膠體粒^平 均直徑爲27奈米。固體物質中的銀含襲由Tc} d^a ( Sdk〇 儀器的產品）測得’相對於在所加入原料中所含有的％質 量％，其爲90質量％。 20 ί紙H度適用中國國家標準（CNS)A4規格（210 X 297公釐_ (請先閱讀背面之注意事項再填寫本頁) · 線· 583288 A7 # _B7___ •五、發明說明（i?) 將3克之銀膠體乙醇溶液部份滴至10平方公分玻璃 板的中央，使用旋轉塗覆技術平均地展開’在第一個階段 係使用旋轉塗覆器以400 rpm進行5秒’且在第二階段則 以600 rpm進行30秒，得到藍銀色的薄膜。將此板置於烤 爐內，於150°C下乾燥10分鐘使溶劑移除。然後’將該板 在250°C下燒烤50分鐘而得到0.5微米厚且具有金屬光澤 之金屬塗層。此金屬塗層的表面電阻性經由Loresta FP ( Mitsubishi化學品公司的產品）測量爲〇·〇5Ω/匚1。 實施例7 在一個500毫升燒瓶內依序加入1.6克Disperbyk-192 (BYK-Chemie的產品），82.4克的1莫耳/升硝酸及82.4克 去離子水。將燒瓶固定於水浴中且將內容物在50°C下攪拌 至Disperbyk-192完全溶解。在持續攪拌下，於溶液中加入 溶解於247.25克去離子水的14.0克硝酸銀，且將混合物在 70°C下進一步攪拌10分鐘。然後，加入36.7克二甲基胺 基乙醇，同時之間溶液迅速轉變爲黑色且溶液溫度昇高至 74°C。靜置該溶液，且當溶液溫度降至70°C時，在相同的 溫度下將溶液攪拌2小時以得到黑黃色的銀膠體水溶液。 將含有反應混合物的容器靜置於60°C的恆溫箱內18 小時，然後置於超濾系統內進行超濾，其中超濾系統之組 裝係使用上述之容器，超濾單元AHP0013 ( Asahi化學工業 公司的產品；截留分子量50000，100單位膜），管式泵和 吸氣器。大約30分鐘之後，由單元中所得到的濾液數量達 到300毫升時，於燒瓶內補充300毫升的去離子水。然後 21 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） (請先閱讀背面之注意事項再填寫本頁) ^_ .線- 583288 A7 r _B7____ *五、發明說明（W ) ，當確定濾液的電導性爲300//S/cm或更低時，將母液濃 縮爲50毫升，因而得到具有25%固體的銀膠體水溶液。 在溶液中的銀膠體粒子平均直徑爲30奈米。固體物質中的 銀含量由TG-DTA (Seiko儀器的產品）測得，相對於在所 加入原料中所含有的85質量％，其爲90質量％。 實施例8 在一個燒杯內加入經硝酸酸化的100毫升0.1莫耳/升 硝酸銀水溶液，然後加入5克Disperbyk-190 (BYK-Chemie 的產品）並溶解。於溶液中加入5毫升之三乙醇胺，因此 得到濃稠亮黃色的銀膠體水溶液。利用離心機將溶液在 3000 G下離心30分鐘而得到銀膠體粒子沈澱物。淸洗步驟 包含丟棄上淸液，加入適量的水，然後在與上述相同的條 件下進行離心。重複此步驟三次而得到85%固體的銀膠體 糊狀物。 將上述的糊狀物以異丙醇稀釋而製備具有20%固體的 溶液，然後固體物質中的銀含量由TG-DTA (Seiko儀器的 產品）測得，相對於在所加入原料中所含有的46質量％， 其爲98質量％。 在實施例1至8中係使用超濾或離心，其中得到金屬 膠體溶液中所含有的金屬膠體粒子濃度相較於個別加入的 原料內所含有者爲增加。此外，在實施例丨和6中，所得 到的高濃縮金屬膠體溶液可非常有利地用於形成具有高電 導性的塗層。 實施例9 22 ί紙張尺度適用中關家標準（CNS)A4規格（210 X 297公爱)---- (請先閱讀背面之注意事項再填寫本頁) li •線· 583288 A7 ，五、發明說明（W ) (請先閱讀背面之注意事項再填寫本頁) 重複實施例1的步驟，除了將Disperbyk-191 (BYK-Chemie的產品）的數量由6.2克增加至21.5克，因此得到 具有30%固體的黃金膠體乙醇溶液。包含黃金膠體粒子和 高分子量顏料分散劑之固體物質中的黃金含量由TG-DTA (Seiko儀器的產品）測得，相對於在所加入原料中所含有 的40質量％，其爲70質量％。 實施例10A7 B7 I ^ ~ V. Description of the invention (2) The description of the invention Γ% first read the unintentional items on the back, and then fill out this page) One object of the present invention is to provide a manufacturing method, which is intended to ensure the stability of the dispersion. When a large amount of high molecular weight pigment dispersant is used, a highly concentrated metal colloid solution showing a high metal concentration can still be obtained. The present invention relates to a method for preparing a highly concentrated metal colloid solution, which comprises partially removing a high molecular weight pigment dispersant from a solution containing metal colloid particles and the high molecular weight pigment dispersant. Partial removal of the high molecular weight pigment dispersant is preferably performed by centrifugation, and more preferably, the centrifugal system is performed at not less than 1000 G. In addition, the partial removal of the high molecular weight pigment dispersant is preferably performed using ultrafiltration, and more preferably, the ultrafiltration is performed using a filtration membrane having a cutoff molecular weight of 3,000 to 80,000. The solution containing the metal colloid particles and the high molecular weight pigment dispersant is preferably obtained by reducing a metal compound in the presence of the high molecular weight pigment dispersant. The metal concentration of the solid matter in the solution containing the metal colloid particles and the high molecular weight pigment dispersant is preferably not more than 85% by mass, and the metal concentration of the solid matter in the highly concentrated metal colloid solution is preferably not less than 90% by mass. The difference between the metal concentration of the solid colloidal solution and the solution containing the metal colloidal particles and the high molecular weight pigment dispersant is preferably not less than 10% by mass. The present invention also relates to a highly concentrated metal colloid solution obtained from the above method. The present invention further relates to a method for using the high-concentration metal glue 4 paper size applicable to Chinese National Standard (CNS) A4 specifications (210 X 297 mm) 583288 _ A7 --------- R7_- DESCRIPTION OF THE INVENTION 0) A coating obtained by a body solution. DETAILED DESCRIPTION OF THE INVENTION The present invention will now be described in further detail. A method for preparing a highly concentrated metal colloidal solution of the present invention includes partially removing a high molecular weight pigment dispersant from a solution containing metal colloidal particles and a high molecular weight pigment dispersant, thereby increasing the metal concentration of its solid matter. The above solution containing metal colloid particles and a high molecular weight pigment dispersant can be obtained by reducing a metal compound in the presence of a high molecular weight pigment dispersant. The metal compound mentioned above is a kind of metal ion that can be released when dissolved in a solvent and A compound that can provide metal colloidal particles when reducing the metal ion. The metal that can be converted into the metal colloidal particles is not particularly limited ', but in order to provide a good conductive coating or a coating having an excellent metallic appearance, it is preferable to use a precious metal or copper. The precious metals mentioned above are not particularly limited, but include gold, silver, ruthenium, rhodium, palladium, hungry, iridium, platinum and the like. Among them, gold, silver, platinum and palladium are preferred. The metal compounds mentioned above are not particularly limited but need to contain any of these metals, and thus include, for example, hydrogen tetrachloroauric acid (dish) · 4H2O (chloroauric acid), silver nitrate, silver acetate, perchloride Acid silver (IV), hydrohexachloroplatinic acid (IV) · 6 out of 0 (chlorouranic acid), potassium chloroplatinate, copper chloride (π) · 2H2O, copper acetate (Π) · 1H2O, copper sulfate (Π), palladium chloride (Π) · 2H20 and rhodium trichloride (melon) · 3 out of 0. They can be used alone or in combination of two or more species. The use ratio of the above metal compounds is preferably the metal in the solvent. 5 The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm). Please read the notes on the back before filling out this page) Γ Order · -1 line-583288 A7 '_B7___. 5. Description of the invention (f) Molar concentration is not less than 0.01 Molar / liter. If the concentration is below 0. 01 mole / liter, the metal mole concentration in the resulting metal colloid solution will be too low to provide effective operation. It is preferably not less than 0. 05 mol / liter, more preferably not less than 0. 1 mole / liter. The solvent mentioned above is not particularly limited, but it needs to be able to dissolve the metal compound, and thus includes, for example, water, organic solvents and the like. The above organic solvents are not particularly limited but include, for example, alcohols having 1 to 4 carbon atoms, such as ethanol, ethylene glycol, etc .; ketones, such as acetone; and esters, such as ethyl acetate, and the like. These solvents can be used alone or in combination of two or more species. When the above-mentioned solvent is a mixture of water and an organic solvent, the organic solvent therein is preferably a water-soluble one, such as acetone, methanol, ethanol, ethylene glycol, and the like. In the practice of the present invention, it is preferred to use a mixed solution of water, alcohol, or water-alcohol, so this type of solvent is suitable for a method of partially removing the high molecular weight pigment dispersant by ultrafiltration in the subsequent stage. The high-molecular-weight pigment dispersant mentioned above is not only a high-molecular-weight polymer incorporating a functional group having high affinity for the pigment surface, but also an amphiphilic copolymer containing a structure having a solvated site, It is generally used as a pigment dispersant in a method for producing a pigment paste. The high-molecular-weight pigment dispersant mentioned above is considered to coexist with the metal colloidal particles, and can stabilize the dispersion liquid of the metal colloidal particles in a solvent. The number average molecular weight of the high molecular weight pigment dispersant is preferably 1,000 to 1,000,000. If it is less than 1000, sufficient dispersion may not be obtained. 6 The paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) (Please read the precautions on the back before filling this page). _- Line-583288 A7 '____ B7___-V. Description of the invention (5) Fluid stability. If it is higher than 1,000,000, the viscosity tends to become too high to ensure good handling. The number average molecular weight is more preferably 2,000 to 500,000, and even more preferably 4,000 to 500,000. The high-molecular-weight pigment dispersant is not particularly limited, but it needs to have the properties mentioned in the foregoing, for example, the compound disclosed in Japanese Laid-Open Publication No. Hei-11-80647. Commercially available products and various compounds can be used as high molecular weight pigment dispersants. Among those commercially available products, mention may be made of, for example, Solsperse 20000, Solsperse 24000, Solsperse 26000, Solsperse 27000, Solsperse 28000, Solsperse 41090 (all products of AVECIA); Disperbyk-160, Disperbyk-161, Disperbyk- 162, Disperbyk-163, Disperbyk-166, Disperbyk-170, Disperbyk-180, Disperbyk-181, Disperbyk-182, Disperbyk-183 »Disperbyk-184 5 Disperbyk-190 5 Disperbyk-191, Disperbyk-192, Disperbyk-2000, Disperbyk-2001 (all BYK-Chemie products), Polymer 100, Polymer 120, Polymer 150, Polymer 400, Polymer 401, Polymer 402, Polymer 403, Polymer 450, Polymer 451, Polymer 452, Polymer 453, EFKA-46, EFKA-47, EFKA-48, EFKA-49, EFKA-1501, EFKA-1502, EFKA-4540, EFKA-4550 (all of which are produced by EFKA Chemicals); FLCJWLEN DOPA-158, FLOWLEN DOPA-22 ^ FLOWLEN DOPA-17 ^ FLOWLEN G-700 ^ FLOWLEN TG-720W, FLOWLEN-730W, FLOWLEN-740W, FLOWLEN-745W (all products of Kyoeisha Chemical Company); Ajisper PA111 7 This paper size is applicable National Standards (CNS) A4 size (210 x 297 mm). "- -------- # 丨 | (Please read the notes on the back before filling this page). ί line · 583288 A7 -___ B7___-5. Description of the invention (6), Ajisper PB711, Ajisper PB811, Ajisper PB821, Ajisper FW911 (all products of Ajinomoto); and Joncryl 678, Joncryl 679, Joncryl 62 (all Johnson polymerization) Company's products). They can be used alone or in combination of two or more species. The amount of the high molecular weight pigment dispersant is preferably not less than 15% by mass based on the combined amount of the metal and the high molecular weight pigment dispersant in the metal compound. If it is less than 15% by mass, sufficient dispersion stability cannot be obtained in the reduction stage, and the effect of increasing the metal concentration is reduced. There is no particular upper limit, but for example, 10 times the mass of the metal in the metal compound can be regarded as the upper limit. The above-mentioned metal compound can be reduced to a metal by reacting a reducing compound therewith in the presence of the high molecular weight pigment dispersant. The above-mentioned reduced compound is preferably an amine. When an amine is added to a solution containing the metal compound and a high molecular weight pigment dispersant and the solution is stirred / mixed, the metal ion system is reduced to metal at about room temperature. By using this amine, the metal compound can be reduced at a temperature of about 5 to 100 ° C, and preferably about 20 to 80 ° C, without the use of extremely dangerous or toxic reducing agents, heating equipment or special radiation equipment . The amines mentioned above are not particularly limited, but compounds such as those mentioned in Japanese Laid-Open Publication No. 11-80647 can be used. Thus, mention may be made of aliphatic amines such as propylamine, butylamine, hexylamine, diethylamine, dipropylamine, dimethylethylamine, diethylmethylamine, triethylamine, ethylenediamine Amine, N, N, N, N'-tetramethylethylenediamine, 1,3-diaminopropane, Ν, N, N'N'-tetramethyl-1,3-diaminopropane , Triethylenetetramine, tetramethylene 8 This paper size applies to Chinese National Standard (CNS) A4 (210 X 297 mm) I ---. -------- i — (Please read the notes on the back before filling this page) Order, --line · 583288 A7 '_ — _B7___, V. Description of the invention (7) ------- --------- (Please read the notes on the back before filling out this page) Ethylpentamine temple; cycloaliphatic amines, for example, Ningding, N-Methylton, Paphine, N , N'-dimethyltonphine, pyrrolidine, N-methylpyrrolidine, etc .; aromatic amines, such as aniline, N-methylaniline, n, N-dimethylaniline, toluidine, Methoxyaniline, ethoxyaniline, etc .; and aralkylamines, such as benzylamine, N-methylbenzylamine, N, N-dimethylbenzylamine, phenethylamine, Xylylenediamine, N, N, N ', N'-tetramethylxylylenediamine and the like. For further examples of the above-mentioned amines, for example, mention may be made of alcohol amines such as methylaminoethanol, dimethylaminoethanol, triethanolamine, ethanolamine, diethanolamine, methyldiethanolamine, Propanolamine, 2- (3-aminopropylamino) ethanol, butanolamine, hexanolamine, dimethylaminopropanol and the like. Among them, alkanolamines are preferred, and dimethylaminoethanol is most preferred. line. In addition to amines, alkali metal borohydrides can also be used, such as sodium borohydride used as a conventional reducing agent; hydrazine compounds; citric acid; tartaric acid; ascorbic acid; formic acid; methyl formaldehyde; dinitrothionites, Hyposulfite derivatives and the like. From the standpoint of applicability, citric acid, tartaric acid or ascorbic acid is preferred. They can be used alone or with the amine, and when the amine is used with citric acid, tartaric acid, or ascorbic acid, citric acid, tartaric acid or ascorbic acid is preferably used in the form of a separate salt. The efficiency of the reduction reaction can be improved when citric acid or hyposulfite derivatives are used with iron (Π) 倂. The amount of the reducing compound to be added is preferably not less than the amount required to reduce the metal present in the metal compound. If it is lower than this amount, the progress of the reduction reaction tends to be incomplete. The upper limit thereof is not particularly limited, but it is preferably not larger than 9 required for reducing the amount of metals present in metal compounds. This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) 583288 A7 ' ___B7____-V. Description of the invention (?) 30 times, more preferably no more than 10 times. ---------------- (Please read the precautions on the back before filling out this page) In addition to the chemical reduction reaction including the addition of this reducing compound, high pressure mercury vapor can also be used in the same way Irradiation technology for lamps. The procedure for adding the reducing compound is not particularly limited, but, for example, the reducing compound may be added after adding a high molecular weight pigment dispersant. In this case, the method for performing the reduction reaction includes dissolving the high molecular weight pigment dispersant in a solvent in advance, adding the reducing compound and the metal compound therein, and adding the rest to the mixture, that is, not in the above steps. The reducing compound or metal compound used. The step of adding the reduced compound includes mixing a high molecular weight pigment dispersant and a reducing compound in advance, and adding the resulting mixture to a solution containing a metal compound. The above reduction results in a solution containing metal colloidal particles having an average particle diameter of about 5 to 100 nm. The solution obtained after this reduction reaction is a colloidal solution containing metal colloidal particles and a high molecular weight pigment dispersant. As used herein, the term "colloid solution" means that the fine metal particles are dispersed in a solvent, and therefore the dispersion can be visually recognized as a solution. The solution obtained after this reduction reaction contains not only metal colloid particles and high molecular weight pigment dispersants, but also other impurity ions, such as chloride ions derived from the raw material of the metal colloid solution, salts derived from the reduction reaction, and according to each case Depending on the amine. Since these impurity ions, salts and amines have an adverse effect on the stability of the resulting metal colloidal solution, it is preferable to remove them. These components can be removed using electrodialysis, centrifugation, ultrafiltration, or similar, but centrifugation and ultrafiltration are better technologies, because these technologies 10 paper standards are applicable to China National Standard (CNS) A4 (210 X 297) (Centi) 583288 A7 * ________ Β7__ —- ~-------------V. Description of the invention (?) The concentration of metals can be increased at the same time, as will be explained below. Γ read the precautions on the back before filling this page.) Furthermore, in the method for preparing the highly concentrated metal colloid solution of the present invention, the metal concentration is increased by partially removing the high molecular weight pigment dispersant. The metal colloid solution used as a matrix for partially removing the high molecular weight pigment dispersant is preferably a solution and the solid matter contained in the metal colloid particles and the high molecular weight pigment dispersant is 0. 05 to 50%. If below 0. 05%, the metal mole concentration will be too low to provide efficient operation. If it exceeds 50%, it is difficult to perform partial removal of the high molecular weight pigment dispersant. Moreover, the metal concentration of the solid substance is preferably not higher than 85% by mass. Partial removal of the high molecular weight pigment dispersant can be effectively performed by centrifugation or ultrafiltration. • Line · In the centrifugation method, metal colloidal particles are produced by Shen Dian, but unnecessary impurities such as ions, salts and amines, and high molecular weight pigment dispersants are still dissolved in the supernatant liquid. Therefore, these components can be removed by discarding the supernatant. The remaining metal colloidal particles can be rinsed by adding a solvent and centrifuged again and again to improve the removal effect. Centrifugation is preferably performed at not less than 1000 G. If it is performed below 1000 G, it is not easy to partially remove the high molecular weight pigment dispersant. The conditions of centrifugation depend on the particle diameter of the metal colloid. For example, when particles with a diameter of nanometer order are to be precipitated, the so-called ultracentrifugation conditions are used. Standard conditions may be 5 to 60 minutes at 3000 G, and more preferably 15 to 45 minutes. The above-mentioned centrifugation method can be changed by the above-mentioned gravity acceleration rate, 11 paper sizes are applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 public love) A7 583288 ___B7___ 5. Description of the invention (/ 0) retention, and / Or the number of operations' classifies the metal colloidal particles according to the particle diameter. By this classification, a highly concentrated metal colloid particle solution having various particle diameters suitable for different uses can be obtained, and at the same time, the diameter of the metal colloid particles can be adjusted to a certain degree. The highly concentrated metal colloid solution obtained by the above-mentioned centrifugation method has an extremely high concentration, so that it is often in the form of a paste. The preferred concentration is usually not less than 80% by mass of solids. The upper limit thereof is not particularly limited, but it is not higher than 90% by mass when the ease of transportation is considered. Ultrafiltration allows the partial removal of high molecular weight pigment dispersants. The membrane used in ultrafiltration (UF) is a finer mesh than the user in microfiltration (MF). Ultrafiltration is usually performed to separate high molecular weight substances from colloidal substances, and its purpose in the present invention is to increase the metal concentration of solid substances in metal colloidal solutions. Generally, substances having a particle diameter of 1 nm to 5 m can be separated by the above-mentioned ultrafiltration. By using the above-mentioned particle diameter as a cut-off point, not only can unnecessary impurities be removed, but salts and amines can also remove high molecular weight pigment dispersants, thereby increasing the metal concentration of solid matter in the metal colloidal solution. If the cut-off point is below 1 nm, the unwanted components will not pass through the filter 'and therefore cannot be removed. If it is higher than 5 m, many metal colloidal particles can easily pass through the filter membrane so that the desired highly concentrated metal colloidal solution cannot be obtained. The filtration membrane used for this ultrafiltration is not particularly limited, but generally a membrane made of a resin material, such as polyacrylonitrile, vinyl chloride-acrylonitrile copolymer, polyboron, polyimide, Polyamide or similar. In these trees ___ 12 This paper size applies the Chinese National Standard (CNS) A4 specification (21 × 297 mm) (Please read the note on the back? Matters before filling out this page) Order-· 583288 A7 ___B7__-V. Invention &Quot; Among the lipid materials, polyacrylonitrile or polymill 'is preferred, and polyacrylonitrile is more preferred. In order to perform the filtration membrane washing which is usually performed after the ultrafiltration can be performed efficiently, it is preferable to use a filtration membrane which allows backwashing for the ultrafiltration. The preferred membranes for ultrafiltration need to retain molecular weights ranging from 3,000 to 80,000. If it is lower than 3000, the undesired high molecular weight pigment dispersant and other substances cannot be sufficiently removed. If it is higher than 80,000 ', the metal colloid particles can easily pass through the filter membrane and the desired metal colloid solution cannot be obtained. A more preferable range is 10,000 to 60,000. "Rejected molecular weight" generally means the molecular weight of polymer molecules that are eliminated through the pores of the ultrafiltration membrane when the polymer solution passes through the ultrafiltration membrane, and is used as a criterion for the pore diameter of the filtration membrane. The higher the amount of retained molecules, the larger the pore diameter of the filter membrane. The geometry of the membrane unit of the ultrafiltration is not particularly limited, but depending on the geometry of the membrane, it may include a hollow sheet unit (also called a capillary unit), a spiral unit, a tubular unit, a plate unit, etc. And any of them can be advantageously used in the operation of the present invention. The larger the membrane area, the easier it is to reduce the filtration time. From the viewpoint of efficiency, it is preferable to use a hollow sheet unit capable of simple filtration. Furthermore, if the number of metal colloidal solutions to be treated is large, it is preferable to use a unit containing a large number of ultrafiltration membrane units. The ultrafiltration method used is not particularly limited, but may include, for example, a conventional method. Generally, a solution containing metal colloidal particles and a high molecular weight pigment dispersant obtained according to the above reaction is passed through an ultrafiltration membrane, thereby removing a filtrate containing impurity ions, a salt'amine and a high molecular weight pigment dispersant. This type of ultrafiltration is usually repeated until the concentration of impurity ions in the filtrate is reduced to the required level. __ 13 This paper size applies to China National Standard (CNS) A4 (210 X 297 public love) --------- ------- (Please read the precautions on the back before filling this page),-Order i-line-583288 A7-____B7 __ _ 5. Description of the invention (A). When performing this operation, it is preferable to add a solvent equivalent to the filtrate to be removed, thereby adjusting the concentration of the metal colloidal solution to be treated to a fixed level. By using a solvent different from that used in the reduction stage, solvent exchange occurs in the metal colloidal solution. The ultrafiltration mentioned above can be carried out using a conventional method ', such as a batch method. The method of batch ultrafiltration involves adding a metal colloid solution to be treated while the ultrafiltration is being performed. After the impurity ions have been removed to the desired concentration level, further ultrafiltration can be performed to increase the solids content. Compared with the solution containing metal colloid particles and high molecular weight pigment dispersant, the metal concentration of the highly concentrated metal colloid solution that can be obtained by centrifugation and / or ultrafiltration has been increased, but the specific metal concentration The number depends on the metal concentration of the solution before processing. Preferably, the metal concentration of the solid matter contained in the metal colloidal particles and the high molecular weight pigment dispersant solution is not higher than 85% by mass before the treatment. The metal concentration is not less than 90% by mass. A preferred difference in metal concentration between the solution before the treatment and the solution after the treatment is less than 10% by mass. The highly concentrated metal colloid solution obtained by centrifugation has a higher solids content than those contained in the solution obtained by ultrafiltration, but in both cases it is preferable to adjust the final solid content to 1 to 50% of gastric volume. Once again, when a solvent different from that used in the reduction stage is used, solvent exchange occurs in the metal colloidal solution. Therefore, the highly concentrated metal colloid solution obtained has a higher metal concentration in the solid material, so it can fully display the inherent properties of the metal. I —— * -------- pi- (Please read first Note on the back, please fill out this page again) Order ·-· · 14 583288 A7 '_ B7 _, V. Description of the invention (0) For example, high electrical conductivity, metallic gloss, dyeing ability, thermal conductivity and the like. In addition, because the concentration of the high molecular weight pigment dispersant in the metal colloidal solution has been reduced to a low level, such a solution is suitable for coating a substrate and forming a metal coating thereon. The coating method of the substrate is not particularly limited, but includes, for example, various conventional methods. The metal coating mentioned above may be a conductive coating or coating having a metallic luster. The above-mentioned metal colloid solution can also be used as a colorant in resin moldings, such as optical materials or coating compositions, and can also be used in such fields as antimicrobial substances, catalysts, cosmetics, electromagnetic shields and the like. According to the preparation method of the present invention, even when a large amount of a high molecular weight pigment dispersant is used in order to ensure the stability of the dispersion liquid, a highly concentrated metal colloid solution showing a high metal concentration can be obtained. The resulting highly concentrated metal colloid solution can be very advantageously used to form metal coatings having electrical conductivity and / or metallic gloss. Best Mode for Carrying Out the Invention The following examples will illustrate the present invention in more detail, but these examples are by no means limiting the scope of the present invention. In the examples,% means% by mass. Example 1In a 2-liter flask, 6. 2 g Disperbyk-191 (product of BYK-Chemie) and 280. 2 grams of ethanol. The flask was fixed in a water bath and the contents were stirred at 50 ° C until Disperbyk-191 was completely dissolved. Add to solution while dissolving in 280 with constant stirring. 2 grams of ethanol 30. 0 grams of chloroauric acid, 15 ί Paper size applies to Chinese National Standard (CNS) A4 (210 X 297 mm)----------------- (Please read the note on the back first Please fill in this page for the matters) · Line-583288 A7 ___B7____ 5. Description of the invention (4) --------------- (Please read the notes on the back before filling this page) and mix the mixture Stir at 50 ° C for 10 minutes. Then, add 32. 4 grams of dimethylaminoethanol, while the solution quickly turned black and the temperature of the solution rose to 63 ° C. The solution was left to stand, and when the temperature of the solution dropped to 50 ° C ', the solution was further stirred at the same temperature for 2 hours to obtain a black-purple yellow gold colloidal ethanol solution. Then, the ultrafiltration unit AHP1010 (a product of Asahi Chemical Industry Co., Ltd .; a molecular weight cut-off of 50,000, 400 unit membranes), a magnetic pump, and a 3 liter stainless steel cup with a tube connector at the bottom were assembled by connecting silica tubes Ultrafiltration system. Place the gold colloidal ethanol solution mentioned above in a stainless steel cup. After adding 2 liters of ethanol, start the pump and begin ultrafiltration. After about 40 minutes, when the amount of filtrate obtained from the unit reached 2 liters, 2 liters of ethanol was replenished in the stainless steel cup. Then, when the conductivity of the filtrate was determined to be 30 // S / cm or lower, the mother liquor was concentrated to 500 ml. -Line Then, a 500 ml stainless steel cup, an ultrafiltration unit AHP0013 (a product of Asahi Chemical Industry Co., Ltd .; a molecular weight cut-off of 50,000, 400 units), a tube pump and an aspirator were used to assemble the ultra-thorium system. The mother liquor obtained above was placed in a stainless steel cup and concentrated to increase the solid content. When the amount of the mother liquor became about 100 ml, the pump was stopped to complete the concentration, thereby obtaining a gold colloidal ethanol solution having 30% solids. The average diameter of the gold colloidal particles in the solution was 22 nm measured by an electron microscope. The gold content in the solid matter containing the gold colloid particles and the high molecular weight pigment dispersant was measured by DTA (a product of Seiko Instruments), and it was 90% by mass relative to 70% by mass contained in the added raw material. 3 grams of the above-mentioned gold colloidal ethanol solution was partially dropped to 10 square centimeters. 16 paper sizes are applicable to China National Standard (CNS) A4 specifications (21〇X 297 public love). ; "-一 -— — 583288 A7 • _B7____ -V. Description of the invention (J) 1 -------- pi — (Please read the precautions on the back before filling this page) The center of the glass plate, The spin-coating technique was used to spread evenly. In the first stage, a spin coater was used for 5 seconds at 400 rpm, and in the second stage, it was performed at 600 rpm for 30 seconds to obtain a slightly black gold film. The plate was placed in an oven and dried at 150 ° C for 10 minutes to remove the solvent. Then, the plate was grilled at 250 ° C for 50 minutes to obtain 0. 7 micron thick metallic coating with metallic luster. The surface resistivity of this metal coating was measured by Loresta FP (a product of Mitsubishi Chemical Co., Ltd.). 〇8Ω / Example 2 Line-Repeat the procedure of Example 1 except that the ultrafiltration unit used in the first test was changed from AHP1010 to ACP1010 (a product of Asahi Chemical Industry Co., Ltd .; the cut-off molecular weight is 13,000, 400 unit membrane), and The ethanol added in the first ultrafiltration test was replaced with an equal amount of deionized water, thereby obtaining a gold colloidal aqueous solution having 30% solids. The average diameter of gold colloidal particles in this solution was 21 nm. The gold content in the solid matter was measured by TG-DTA (a product of Seiko Instruments) and was 90% by mass with respect to 70% by mass contained in the added raw material. Example 3In a 500 ml flask was added 4. 9 grams of EFKA 4550 (product of EFKA Chemicals), 112. 1 gram ethanol and 13. 0 g of dimethylaminoethanol. The flask was fixed in a water bath and the contents were stirred at 50 ° C. for about 10 minutes until EFKA 4550 was completely dissolved. Under continuous stirring, dissolved in 112. 1 gram of ethanol 12. 0 g of chloroauric acid, during which time the solution quickly turned black and the solution temperature rose to 58 ° C. Allow the solution to stand, and the 17 paper sizes shall comply with the Chinese National Standard (CNS) A4 (210 X 297 mm) 583288 A7 __ B7______-V. Description of the invention (Μ) When the temperature of the solution drops to 50 ° C, The solution was further stirred at the same temperature for 2 hours to obtain a black-violet gold colloidal ethanol solution. Then, a 500 ml stainless steel cup, an ultrafiltration unit AHP0013 (a product of Asahi Chemical Industry Co., Ltd .; a molecular weight cut-off of 50,000, 100 units of membrane), a tube pump, and an aspirator were used to assemble the ultramarine system. The gold colloidal ethanol solution obtained above was placed in a stainless steel cup and the operation of ultrafiltration was started. After about 30 minutes, when the amount of filtrate obtained in the unit reached 300 ml, 300 ml of ethanol was replenished in a stainless steel cup. Then, when the conductivity of the filtrate was determined to be 30 // S / cm or lower, the mother liquor was concentrated to 50 ml, thereby obtaining a gold colloidal ethanol solution with 25% solids. Gold colloid particles in solution had an average diameter of 24 nm. The gold content of a solid substance containing gold colloid particles and a high molecular weight pigment dispersant was measured by TG-DTA (a product of Seiko Instruments), and it was 90% by mass with respect to 70% by mass contained in the added raw material. Example 4 In a 500 ml flask was added 4.6 grams of Disperbyk-184 (product of BYK-Chemie), 112. 1 g of deionized water and 13. 0 g of dimethylaminoethanol was stirred at room temperature for about 10 minutes. With continuous stirring, the solution was added to dissolve in 112. 1 gram of deionized water 0 g of chloroauric acid, during which time the solution quickly turned black and the solution temperature rose to 20 ° C to 28 ° C. The stirring was continued for 2 hours, whereby a black-purple gold colloidal aqueous solution was obtained. Then, use a 500ml stainless steel cup, ultrafiltration unit AHP0013 (product of Asahi Chemical Industry Co., Ltd .; cut-off molecular weight 50000, 100 units 18) This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) (Please read first Note on the back, please fill out this page again) --line-583288 A7, ___B7 _, 5. Description of the invention (卩) Membrane), tube pump and aspirator equipped with ultrafiltration system. The gold colloidal aqueous solution obtained above was placed in a stainless steel cup and the operation of ultrafiltration was started. After about 30 minutes, when the amount of filtrate obtained from the unit reached 300 ml, 300 ml of deionized water was replenished in a stainless steel cup. When the conductivity of the filtrate was determined to be 300 // S / cm or lower, the mother liquor was concentrated to 50 ml, thereby obtaining a gold colloidal aqueous solution having a solid content of 25%. Gold colloid particles in solution had an average diameter of 25 nm. The gold content in a solid substance containing gold colloidal particles and a high molecular weight pigment dispersant was measured by TG-DTA (product of Seiko Instruments), and it was 90% by mass with respect to 70% by mass contained in the added raw material. Example 5In a 2 liter flask was added 14. 0 g Disperbyk-190 (product of BYK · Chemie), 294. 3 grams of 1 mol / L nitric acid, and 294. 3 grams of deionized water. The flask was fixed in a water bath and the contents were stirred at 50 ° C until Disperbyk-190 was completely dissolved. Add to the solution and dissolve in 883 with constant stirring. 0 grams of deionized water of 50. 0 g of silver nitrate, and the mixture was further stirred at 70 ° C. for 10 minutes. Then, add 131. 0 g of dimethylaminoethanol, while the solution rapidly changed to black and the solution temperature rose to 76t. The solution was left to stand, and when the temperature of the solution dropped to 70 ° C, the solution was further stirred at the same temperature for 2 hours to obtain a black-yellow silver colloidal aqueous solution. The reaction mixture was transferred to a 1-liter plastic bottle and allowed to stand in a 60 ° C incubator for 18 hours. Then, the ultrafiltration unit AHP1010 (a product of Asahi Chemical Industry Co., Ltd .; a molecular weight cut-off of 50,000, 400 unit membranes), a magnetic pump, and a 3 liter stainless steel cup with a tube connector at the bottom, were borrowed from silicon and oxygen. Standard (CNS) A4 specification (210 X 297 mm) (Please read the precautions on the back before filling out this page) Order · -line-583288 A7 will _____B7__ • 5. Description of the invention () Alkanes are connected to each other and assembled Ultrafiltration system. Place the reaction mixture mentioned above in a 60 ° C incubator for 18 hours in a stainless steel cup. After adding 2 liters of deionized water, start the pump and begin ultrafiltration. After about 40 minutes, when the amount of filtrate obtained from the unit reached 2 liters, 2 liters of deionized water was replenished in the stainless steel cup. Then, when the conductivity of the filtrate was determined to be 300 // S / cm or lower, the mother liquor was concentrated to 500 ml. Then, an ultrafiltration system was assembled using a 500 ml stainless steel cup, an ultrafiltration unit AHP0013 (a product of Asahi Chemical Industry Co., Ltd .; a molecular weight cut-off of 50,000, 100 units), a tube pump, and an aspirator. The mother liquor obtained above was placed in a stainless steel cup and concentrated to increase the solid content. When the amount of mother liquor reached about 100 ml, the pump was stopped to complete the concentration, thereby obtaining a silver colloidal aqueous solution having a solids content of 30%. The average diameter of the silver colloidal particles in the solution was 27 nm. The silver content in the solid matter was measured by TG_DTA (a product of Seik0 Instruments) 'and was sealed at 85% by weight contained in the added raw material, which was 90% by mass. Example 6 The procedure of Example 5 was repeated except that the ultrafiltration unit used in the first ~ test was changed from AHP1010 to ACP1010 (product of ASahi Chemical Industry Co., Ltd .; the cut-off molecular weight was 13,000, 400 unit membrane), and The deionized water of A added in the furnace test was replaced with an equal amount of ethanol, thus obtaining a silver colloidal ethanol solution with 30% solids. The average diameter of the silver colloidal particles in this solution was 27 nm. The silver content in the solid matter was measured by Tc} d ^ a (a product of the Sdko instrument) and it was 90% by mass relative to the% mass% contained in the added raw material. 20 ί Paper H degree applies Chinese National Standard (CNS) A4 specification (210 X 297 mm_ (Please read the precautions on the back before filling out this page) · Line · 583288 A7 # _B7___ • V. Description of the invention (i?) A 3 g portion of the silver colloidal ethanol solution was dropped to the center of a 10 cm2 glass plate, and spread evenly using a spin coating technique 'in the first stage, using a spin coater at 400 rpm for 5 seconds' and in the second stage, The stage is performed at 600 rpm for 30 seconds to obtain a blue-silver film. This plate is placed in an oven and dried at 150 ° C for 10 minutes to remove the solvent. Then the plate is grilled at 250 ° C for 50 minutes And get 0. 5 micron thick metallic coating with metallic luster. The surface resistivity of this metal coating was measured by Loresta FP (a product of Mitsubishi Chemical Co., Ltd.) to be 0.05 Ω / 匚 1. Example 7In a 500 ml flask, 1. 6 g Disperbyk-192 (product of BYK-Chemie), 82. 4 grams of 1 mol / L nitric acid and 82. 4 grams of deionized water. The flask was fixed in a water bath and the contents were stirred at 50 ° C until Disperbyk-192 was completely dissolved. Under continuous stirring, added to the solution and dissolved in 247. 25 grams of deionized water 14. 0 g of silver nitrate, and the mixture was further stirred at 70 ° C for 10 minutes. Then, add 36. 7 grams of dimethylaminoethanol, while the solution quickly turned black and the solution temperature rose to 74 ° C. The solution was left to stand, and when the temperature of the solution dropped to 70 ° C, the solution was stirred at the same temperature for 2 hours to obtain a black-yellow silver colloidal aqueous solution. Place the container containing the reaction mixture in an incubator at 60 ° C for 18 hours, and then place it in an ultrafiltration system for ultrafiltration. The ultrafiltration system is assembled using the above-mentioned container. The ultrafiltration unit AHP0013 (Asahi Chemical Industry The company's products; cut-off molecular weight of 50,000, 100 unit membrane), tube pumps and aspirators. After about 30 minutes, when the amount of filtrate obtained in the unit reached 300 ml, the flask was replenished with 300 ml of deionized water. Then 21 paper sizes are applicable to Chinese National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling this page) ^ _. Line-583288 A7 r _B7____ * V. Description of the Invention (W), when the conductivity of the filtrate is determined to be 300 // S / cm or lower, the mother liquor is concentrated to 50 ml, thereby obtaining a silver colloidal aqueous solution with 25% solids . The average diameter of the silver colloidal particles in the solution was 30 nm. The silver content in the solid matter was measured by TG-DTA (a product of Seiko Instruments) and was 90% by mass with respect to 85% by mass contained in the added raw material. Example 8In a beaker was added 100 ml of 0.1 ml acidified with nitric acid. 1 mol / L silver nitrate in water, then 5 g of Disperbyk-190 (product of BYK-Chemie) was added and dissolved. 5 ml of triethanolamine was added to the solution, thereby obtaining a thick and bright yellow colloidal silver aqueous solution. The solution was centrifuged at 3000 G for 30 minutes with a centrifuge to obtain a silver colloidal particle precipitate. The rinsing step involves discarding the supernatant, adding an appropriate amount of water, and then centrifuging under the same conditions as above. This step was repeated three times to obtain a silver colloid paste of 85% solids. The above paste was diluted with isopropanol to prepare a solution with 20% solids, and then the silver content in the solid matter was measured by TG-DTA (product of Seiko Instruments) with respect to 46% by mass, which was 98% by mass. In Examples 1 to 8, ultrafiltration or centrifugation was used, and the concentration of metal colloid particles contained in the obtained metal colloid solution was increased compared to those contained in the raw materials added separately. In addition, in Examples 丨 and 6, the obtained highly concentrated metal colloid solution can be very advantageously used to form a coating having high conductivity. Example 9 22 The paper size applies the Zhongguanjia Standard (CNS) A4 specification (210 X 297 public love) ---- (Please read the precautions on the back before filling this page) li • line · 583288 A7, five, Description of the Invention (W) (Please read the notes on the back before filling this page) Repeat the steps of Example 1 except that the number of Disperbyk-191 (product of BYK-Chemie) is changed from 6. 2 grams increased to 21. 5 grams, thus giving a gold colloidal ethanol solution with 30% solids. The gold content in a solid substance containing gold colloid particles and a high molecular weight pigment dispersant was measured by TG-DTA (a product of Seiko Instruments), and it was 70% by mass based on 40% by mass contained in the added raw material. Example 10
重複實施例1的步驟，除了將第一次試驗中所使用的 超濾單元由AHP1010換成ACP1010 (Asahi化學工業公司 的產品；截留分子量13000，400單位膜），且將第—次超 濾試驗所加入的乙醇以等量的去離子水取代，因此得到具 有30%固體的黃金膠體水溶液。在此溶液中的黃金膠體粒 子平均直徑爲21奈米。固體物質中的黃金含量由T(}_DTA (Seiko儀器的產品）測得，相對於在所加入原料中所含有 的40質量％，其爲55質量％。 23 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐）The procedure of Example 1 was repeated, except that the ultrafiltration unit used in the first test was changed from AHP1010 to ACP1010 (a product of Asahi Chemical Industry Co., Ltd .; the cut-off molecular weight was 13,000, 400 unit membrane), and the first ultrafiltration test The added ethanol was replaced with an equal amount of deionized water, thereby obtaining a gold colloidal aqueous solution having 30% solids. The average diameter of the gold colloidal particles in this solution was 21 nm. The gold content in solid matter is measured by T (} _ DTA (a product of Seiko Instruments), which is 55% by mass relative to the 40% by mass contained in the added raw materials. 23 This paper size applies the Chinese National Standard (CNS ) A4 size (210 X 297 mm)