1236931 A7 _B7_ 五、發明説明（1 ) 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，可形成金屬薄膜之金屬氧化物分散 體’及利用該分散體於基板上形成金屬薄膜之方法。又， 本發明亦係有關於多孔性金屬薄膜之製造方法。 先行技術 於基板上形成金屬薄膜之方法，向來習知有真空蒸鍍 法、濺鍍法、CVD法、鍍層法、金屬糊法等。其中，真空 蒸鍍法、濺鍍法、CVD法均有須昂貴之真空設備，且成膜 速度慢之問題。 以鍍層法於具導電性之基材上雖相較易於形成金屬薄 膜，但欲形成於絕緣基材上，因須先形成導電層，其程序 變得煩雜。且因鍍層法利用到溶液中之反應，產生大量廢 液，其處理費事，成本亦高。 經濟部智慧財產局員工消費合作社印製 金屬糊法係將金屬粒子分散於溶劑塗布於基材上，加 熱得金屬薄膜之方法，不須真空設備等特殊裝置，程序簡 化係其優點，但金屬粒子之熔化通常須有1000°C以上之高 溫°因此，基材限於陶瓷等具耐熱性之基材，且易有基材 因熱受損，經加熱產生殘留應力致基材損傷等問題。 另一方面，降低金屬粒子之粒徑，以降低金屬糊之煅 燒溫度之技術已爲所知。例如專利第2561537號說明書揭 示’利用粒徑1 00奈米以下之金屬微粒子之分散體形成金 屬薄膜之方法。然而，其所需之100奈米以下的金屬粒子 之製造方法，係將低壓下揮發之金屬蒸氣快速冷卻之方法 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐〉 -5- 1236931 經濟部智慧財產局員工消費合作社印製 A7 B7•五、發明説明（2 ) ，難以大量生產，並有金屬粒子成本非常之高的問題。金 屬氧化物粒子分散而成的金屬氧化物糊用於形成金屬薄膜 之方法亦係已知。日本專利特開平5 - 9 8 1 9 5號公報揭示’加 熱含結晶性高分子，粒徑300奈米以下之金屬氧化物分散 而成的金屬氧化物糊，使結晶性高分子分解，得金屬薄膜 之方法。然而，該方法須先分散300奈米以下之金屬氧化 物於結晶性高分子中，極其費事以外，結晶性高分子之分 解須400°C至900°C之高溫。因此，可用基材須具該溫度以 上之耐熱性，有可用基材受限之問題。 如上，以金屬粒子或金屬氧化物之分散體塗布於基板 上，經加熱處理得金屬薄膜之方法，製程成本低。但使用 金屬粒子之方法，有粒子極其昂貴之問題。而使用金屬氧 化物粒子之方法，須先將粒子分散於結晶性高分子中，焚 化結晶性高分子所須加熱處理有溫度高之問題，目前尙未 實用化。尤以在消費產品領域所用之樹脂基材上的金屬薄 膜之形成更難以採用。另一方面，以較低溫作加熱處理則 難得多孔性之金屬薄膜。 金屬多孔體膜之製造方法，已知有鍍層法、漿體法。 .鍍層法係以碳粉等附著於聚氨酯泡棉等發泡樹脂骨架表面 賦予導電性，於其上鍍出金屬，然後焚化發泡樹脂及碳粉 ，得金屬多孔體之方法。然而該方法製程煩雜。另一方面 ，漿體法係以金屬粉末或金屬纖維浸滲塗布於聚氨酯等發 泡樹脂骨架表面’然後加熱焚化樹脂成分燒結金屬粉末得 金屬多孔體之方法。該方法因浸滲於多孔性樹脂，原料金 本紙¥尺度適用中國國家標準(CNS ) A4規格（210X297公着) (請先閱讀背面之注意事項再填寫本頁) -6- 1236931 經濟部智慧財產局員工消費合作社印製 A7 ______B7五、發明説明（3 ) 屬粉末或金屬纖維粒徑須小，通常在數十微米至數百微米 。然而，小粒徑金屬粉末之製造，須熔融金屬之噴霧、粉 碎等煩雜製程，故原料昂貴。又，小粒徑之金屬粉末因表 面積大，有引燃、***之危險，故製造設備成本高。又再 ，所得多孔體之孔徑因反映所浸滲之發泡樹脂之孔徑，在 數十微米以上。 不用金屬粉末，以金屬氧化物粉末與樹脂粘結劑混合 •，以模具形成特定形狀，再於氧化性環境氣體中加熱，焚 化樹脂粘結劑得多孔性金屬氧化物燒結體，隨後於還原性 環境氣體中煅燒以得金屬多孔體之方法亦係已知（特開平5 -195110號公報）。然而，該方法雖有能以廉價金屬氧化物原 料製作孔徑約1微米之小孔徑金屬多孔體之優點，但因須 加壓過程，有製程煩雜之問題。並且，用作樹脂結合劑之 樹脂係聚乙烯醇樹脂、縮丁醛樹脂、壓克力樹脂等親水性 樹脂，欲完全焚化壓縮狀態下之此等粘結劑須1 000°C以上 之高溫，必須要有高溫煅燒設備，係製造設備上之問題。 金屬氧化物粉末與有機粘結劑混合’不經加壓成形， 於還原氣體中煅燒，因有機粘結劑不在壓縮環境下，可於 較低溫，例如使用聚乙烯醇粘結劑時之700°C去除（特表 2 0 0 0 - 5 0 0 8 2 6號公報）。但因金屬氧化物粒子間未經壓縮， 還原得之金屬粒子間不相熔合’僅得造粒之金屬粉末，不 得金屬多孔體。 亦即，使用金屬氧化物’不經加壓過程等煩雜過程’ 且以低溫得1微米以下小孔徑之多孔性金屬薄膜之方法’ 本紙張尺度適用中國國家標準（CNS ) A4規格（210X29*7公釐） (請先閱讀背面之注意事項再填寫本頁) £ 訂 1236931 A7 B7 五、發明説明（4 ) . 尙未存在。 (請先閱讀背面之注意事項再填寫本頁) 因而，本發明之課題即在提供廉價，以低溫加熱處理 ’可於基材上形成密合性高之薄膜的金屬氧化物分散體， 及使用該金屬氧化物分散體，於基材上製造金屬薄膜之方 法。又，亦提供多孔性金屬薄膜之製造方法。 發明之揭示 本發明人爲解決上述課題精心探討，終於完成本發明 〇 亦即，本發明如下。 ' 1.含粒徑不及200奈米之金屬氧化物及分散媒體之金屬 氧化物分散體，其分散媒體含多元醇及/或聚醚化合物。 2. 上項1之金屬氧化物分散體，其中多元醇之碳原子數 在10以下。 3. 上項1或2之金屬氧化物分散體，其中多元醇係糖醇 〇 經濟部智慧財產局員工消費合作社印t 4·上項1至3中任一項之金屬氧化物分散體，其中聚醚 化合物係以碳原子數2至8之直鏈及環狀氧化烯基爲重複 單元之脂族聚醚。 5. 上項1至4中任一項之金屬氧化物分散體，其中聚醚 化合物之分子量在150以上600以下。 6. 上項5之金屬氧化物分散體，其中聚醚化合物係分子 量250以上1 500以下之聚乙二醇及/或聚丙二醇。 7 ·上項1至6中任一項之金屬氧化物分散體，其中由金 本紙張尺度適用中國國家標準( CNS ) A4規格（210X297公整) " — -8- 1236931 A7 __ B7____ 五、發明説明（5 ) 屬氧化物還原得之金屬，體積電阻値在1X 10“歐姆公分以 下。 . 8·上項1至7中任一項之金屬氧化物分散體，其中金屬 氧化物係氧化銅或氧化銀。 9. 上項8之金屬氧化物分散體，其中金屬氧化物係氧化 亞銅。 10. 上項1至9中任一項之金屬氧化物分散體，其中金 屬氧化物之含量，占金屬氧化物分散體爲總重量之5至90 重量％。 11·上項1至10中任一項之金屬氧化物分散體，其中含 金屬粉，並且該金屬粉與金屬氧化物微粒合計占金屬氧化 物分散體總重量的5重量％以上9Q重量％以下。 : 12·上項11之金屬氧化物分散體，其中上述金屬粉含至 少一種選自金、銀、銅、钯、銷、鎳、鉻、錦、錫、鋅、 鈦、鎢、組、鋇、铑、釕、餓、鉍、銥、鈷、銦、鐵、鉛 所成群之金屬。 13·上項1至12中任一項之金屬氧化物分散體，其中含 熱固性樹脂，其占金屬氧化物分散體總重量之1至20重量 %。 14. 上項1至13中任一項之金屬氧化物分散體，其中含 除多元醇及聚醚化合物以外，含可還原金屬氧化物之還原 劑，其占金屬氧化物分散體總重量之0.1至70重量％。 15. 上項1至14中任一項之金屬氧化物分散體，其中多 元醇之含量係占金屬氧化物分散體總重量0.1重量％以上95 本紙張尺度適用中國國家標隼（CNS ) A4規格（210X297公釐） ~ (請先閱讀背面之注意事項再填寫本頁) -裝-1236931 A7 _B7_ V. Description of the invention (1) Technical field (please read the precautions on the back before filling out this page) The present invention relates to a metal oxide dispersion that can form a metal thin film and use the dispersion on a substrate Method for forming metal thin film. The present invention also relates to a method for producing a porous metal thin film. A prior art method of forming a metal thin film on a substrate has conventionally been known as a vacuum evaporation method, a sputtering method, a CVD method, a plating method, and a metal paste method. Among them, the vacuum evaporation method, the sputtering method, and the CVD method have the problems of requiring expensive vacuum equipment and slow film formation. Although it is relatively easy to form a metal thin film on a conductive substrate by the plating method, if it is to be formed on an insulating substrate, a conductive layer must be formed first, and the procedure becomes complicated. In addition, due to the reaction of the solution in the plating method, a large amount of waste liquid is generated, which is laborious and expensive. The method of printing metal paste by the employee's consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs is the method of dispersing metal particles in a solvent and coating it on a substrate and heating it to obtain a metal film. Special equipment such as vacuum equipment is not required. The simplified procedure is its advantage, but metal particles The melting must usually have a high temperature above 1000 ° C. Therefore, the substrate is limited to substrates with heat resistance such as ceramics, and it is prone to problems such as damage to the substrate due to heat and residual stress caused by heating. On the other hand, a technique for reducing the particle diameter of the metal particles to reduce the firing temperature of the metal paste is known. For example, Patent No. 2561537 discloses a method for forming a metal thin film using a dispersion of metal fine particles having a particle size of 100 nm or less. However, the manufacturing method of the metal particles below 100 nanometers required is a method of rapidly cooling metal vapors volatilized under low pressure. The paper size is applicable to China National Standard (CNS) A4 specification (210X 297 mm> -5- 1236931 A7 B7 printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs • V. Invention Description (2), it is difficult to mass-produce, and there is a problem that the cost of metal particles is very high. For metal oxide pastes in which metal oxide particles are dispersed A method for forming a metal thin film is also known. Japanese Patent Laid-Open No. 5-9 8 1 9 5 discloses a metal oxide obtained by dispersing a metal oxide containing a crystalline polymer and having a particle diameter of 300 nm or less. Paste to decompose the crystalline polymer to obtain a metal thin film. However, this method must first disperse metal oxides below 300 nanometers in the crystalline polymer, which is extremely troublesome. The decomposition of the crystalline polymer must be 400 High temperature from ° C to 900 ° C. Therefore, the usable substrate must have heat resistance above this temperature, and there is a problem that the usable substrate is limited. As above, metal particles or metal oxides are used. The method in which the dispersion is coated on a substrate and heated to obtain a metal thin film has a low manufacturing cost. However, the method using metal particles has the problem that the particles are extremely expensive. In the method using metal oxide particles, the particles must be dispersed in the crystal first Among the high-molecular polymers, the heat treatment required for incineration of crystalline polymers has a problem of high temperature, which has not yet been put into practical use. The formation of metal thin films on resin substrates used in the field of consumer products is more difficult to adopt. On the other hand, Porous metal thin films are difficult to obtain by heating at a lower temperature. There are known methods for producing porous metal films such as the plating method and the slurry method. The coating method is a method in which carbon powder is attached to a foamed resin skeleton such as polyurethane foam. The method of imparting conductivity to the surface, plating metal on it, and then incinerating the foamed resin and carbon powder to obtain a porous metal body. However, the method has a complicated process. On the other hand, the slurry method is impregnated with metal powder or metal fibers. A method of coating on the surface of a foamed resin skeleton such as polyurethane, and then heating and incinerating a resin component to sinter a metal powder to obtain a porous metal body. The method is impregnated with porous resin, and the size of the original paper is applicable to the Chinese National Standard (CNS) A4 (210X297) (please read the precautions on the back before filling this page) -6- 1236931 Intellectual Property Bureau, Ministry of Economic Affairs Printed by employees' consumer cooperatives A7 ______B7 V. Description of invention (3) The diameter of the powder or metal fibers must be small, usually tens of micrometers to hundreds of micrometers. However, the manufacture of small-sized metal powders requires the spraying of molten metal, Crushing and other complicated processes make raw materials expensive. In addition, metal powders with small particle sizes have high surface area, which may ignite and explode, so the cost of manufacturing equipment is high. Furthermore, the pore diameter of the obtained porous body reflects the infiltration process. The pore diameter of the foam resin is more than tens of microns. Instead of metal powder, metal oxide powder is mixed with the resin binder, and a specific shape is formed by a mold, and then heated in an oxidizing ambient gas to incinerate the resin binder to become porous. A method of obtaining a porous metal body by sintering a basic metal oxide and then calcining it in a reducing ambient gas is also known (Japanese Patent Application Laid-Open No. 5-195110). However, although this method has the advantage of being able to produce a small-pore metal porous body having a pore diameter of about 1 micron from a cheap metal oxide raw material, there is a problem that the manufacturing process is complicated because a pressurization process is required. In addition, resins such as polyvinyl alcohol resins, butyral resins, and acrylic resins, which are used as resin binders, must be at a high temperature of 1 000 ° C or higher in order to completely incinerate these adhesives in a compressed state. There must be high temperature calcining equipment, which is a problem in manufacturing equipment. The metal oxide powder is mixed with the organic binder without forming under pressure and calcined in a reducing gas. Because the organic binder is not in a compressed environment, it can be used at a lower temperature, such as 700 ° when using a polyvinyl alcohol binder. C is removed (special table 2 0 0-5 0 0 8 2 6). However, since the metal oxide particles are not compressed, the reduced metal particles are not fused with each other ', so that only granulated metal powder can be obtained, and no porous metal body can be obtained. That is, a method for obtaining a porous metal film with a small pore diameter of less than 1 micron at a low temperature by using a metal oxide 'without complicated processes such as pressurization process' This paper size is applicable to China National Standard (CNS) A4 specification (210X29 * 7 (Mm) (Please read the notes on the back before filling out this page) £ Order 1236931 A7 B7 V. Description of Invention (4). 尙 Does not exist. (Please read the precautions on the back before filling this page) Therefore, the problem of the present invention is to provide a low-cost, low-temperature heat treatment, which can form a metal oxide dispersion with high adhesion on the substrate, and use The metal oxide dispersion is a method for manufacturing a metal thin film on a substrate. A method for producing a porous metal thin film is also provided. Disclosure of the Invention The present inventors have carefully studied in order to solve the above problems, and finally completed the present invention. That is, the present invention is as follows. '1. A metal oxide dispersion containing a metal oxide with a particle size of less than 200 nm and a dispersion medium containing a polyol and / or a polyether compound. 2. The metal oxide dispersion of the above item 1, wherein the number of carbon atoms of the polyol is 10 or less. 3. The metal oxide dispersion of item 1 or 2 above, in which the polyhydric alcohol is a sugar alcohol. The employee's cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs has printed t 4. The metal oxide dispersion of any one of items 1 to 3 above, where The polyether compound is an aliphatic polyether having linear and cyclic oxyalkylene groups having 2 to 8 carbon atoms as repeating units. 5. The metal oxide dispersion according to any one of the above items 1 to 4, wherein the molecular weight of the polyether compound is 150 or more and 600 or less. 6. The metal oxide dispersion of item 5 above, wherein the polyether compound is polyethylene glycol and / or polypropylene glycol having a molecular weight of 250 to 1,500. 7 · The metal oxide dispersion of any one of items 1 to 6 above, in which the Chinese paper standard (CNS) A4 specification (210X297 round) is applied from the gold paper size " — -8- 1236931 A7 __ B7____ V. Description of the invention (5) It is a metal obtained by reduction of oxides with a volume resistance 値 below 1X 10 "ohm centimeters. .8. The metal oxide dispersion of any one of items 1 to 7 above, wherein the metal oxide is copper oxide Or silver oxide. 9. The metal oxide dispersion of the above item 8, wherein the metal oxide is cuprous oxide. 10. The metal oxide dispersion of any one of the above items 1 to 9, wherein the content of the metal oxide is 5 to 90% by weight of the total weight of the metal oxide dispersion. 11. The metal oxide dispersion according to any one of the above 1 to 10, which contains metal powder, and the metal powder and metal oxide fine particles together account for 5 to 9% by weight of the total weight of the metal oxide dispersion: 12. The metal oxide dispersion of the above item 11, wherein the metal powder contains at least one selected from the group consisting of gold, silver, copper, palladium, pins, nickel , Chromium, brocade, tin, zinc, titanium, tungsten, group, , Rhodium, ruthenium, bismuth, bismuth, iridium, cobalt, indium, iron, lead. 13. The metal oxide dispersion of any one of items 1 to 12 above, which contains a thermosetting resin, which accounts for metal 1 to 20% by weight of the total weight of the oxide dispersion. 14. The metal oxide dispersion according to any one of 1 to 13 above, which contains a reduction of a reducible metal oxide in addition to a polyol and a polyether compound. Agent, which accounts for 0.1 to 70% by weight of the total weight of the metal oxide dispersion. 15. The metal oxide dispersion of any one of the above items 1 to 14, wherein the content of the polyol is the total weight of the metal oxide dispersion 0.1% by weight or more 95 This paper size is applicable to China National Standard (CNS) A4 specification (210X297 mm) ~ (Please read the precautions on the back before filling this page) -pack-
、1T 經濟部智慧財產局員工消費合作社印製 1236931 經濟部智慧財產局員工消費合作社印製 A7 _ B7 ____.五、發明说明（6 ) 重量％以下。 i 6.上項1至1 5中任一項之金屬氧化物分散體，其中聚 醚化合物之含量係占金屬氧化物分散體總重量的0.1至70 重量％。 1 7 .上項1至1 5中任一項之金屬氧化物分散體，其中聚 醚化合物之含量占金屬氧化物分散體總重量不及0.1重量％ 〇 1 8 ·煅燒上項1 6之金屬氧化物分散體所得，多數一次粒 徑不及200奈米之金屬微粒集結，接觸部份熔合形成之金 *屬薄膜。 1 9 .上項1 7之金屬氧化物分散體煅燒而得，多數一次粒 徑不及2 〇 0奈米之金屬微粒集結，接觸部份熔合形成之具 多孔構造的金屬薄膜。 2〇.包含將上項1至16中任一項之金屬氧化物分散體塗 布於基板後作加熱處理的金屬薄膜製造方法。 2 1.上項2 0之金屬薄膜製造方法，其中包含，於非氧化 性環境氣體中作加熱處理。 22. 上項2〇之金屬薄膜製造方法，其中包含，以金屬氧 .化物分散體塗布於基板後，於鈍性環境氣體中加熱锻燒， 隨後在還原性環境氣體中加熱煅燒。 23. 上項20至22中任一項之金屬薄膜製造方法，其中 加熱處理溫度在50°C以上500°C以下。 發明之最佳實施形態 本紙張尺度適用中國國家標準（CNS ) A4規格（210 '<297公^]--------- -10- (請先閱讀背面之注意事項再填寫本頁) 1236931 經濟部智慧財產局員工消費合作社印製 A7 B7五、發明説明（7 ) . 以下詳細說明本發明。 如上述，本發明之金屬氧化物分散體包含粒徑不及200 奈米之金屬氧化物及分散媒體等必要成分。又，本發明金 屬氧化物分散體，其特徵爲：分散媒體包含多元醇及/或 聚醚化合物。以下說明此等成分。 用於本發明之金屬氧化物，其粒徑不及200奈米，不 及100奈米爲較佳，不及30奈米又更佳。在此，粒徑指一 次粒徑，可藉電子顯微鏡等之形態觀察測定。粒徑不及 200奈米時因金屬氧化物還原得之金屬微粒小，其表面能量 變大，熔點下降，金屬粒子間應可藉低溫熔合形成金屬薄 '膜。金屬氧化物粒徑愈小，金屬氧化物粒子之還原變容易 ，故由還原難易之觀點，金屬氧化物粒子愈小愈佳。金屬 氧化物之粒徑在20 0奈米以上時，還原處理所得金屬粒子 間之熔合不足，不得緻密強固之結構體。另一方面，粒徑 不及1 00奈米時因可用作擠出微小液滴形成微細配線之噴 墨法的導電墨料，適用於不經蝕刻處理之微細電路的形成 〇 金屬氧化物若係經加熱處理可還原者均可使用。各金 屬氧化物粒子由單一金屬氧化物構成亦可，由多數之金屬 氧化物構成之複合金屬氧化物亦佳。還原金屬氧化物而得 之金屬，其體積電阻値以lx 10“歐姆公分以下爲佳，lx 10·5歐姆公分以下更佳。使用如此之金屬氧化物因所得金屬 薄膜之導電性高故較佳。此類金屬氧化物有例如氧化銀、 氧化銅、氧化鈀、氧化鎳、氧化鉛、氧化鈷等。其中，因 本紙浪尺度適用中國國家標準（CNS ) A4規格（210X297公釐） (請先閱讀背面之注意事項再填寫本頁) -11 - 1236931 A7 B7 五、發明説明（8 ) (請先閱讀背面之注意事項再填寫本頁) 容易還原且還原後導電度高，以氧化銅及氧化銀爲特佳。 銀氧化物有氧化第一銀、氧化第二銀及氧化第三銀等，銀 之氧化態無限，基於粒子之安定性，以氧化第一銀爲佳。 銅氧化物有氧化亞銅及氧化銅等，銅之氧化態無限，因易 於還原成金屬銅，以氧化亞銅爲特佳。 此等金屬氧化物可用市售品，亦可利用已知合成方法 合成。市售品有CI化成（股）之平均粒徑約30奈米（標稱）之 氧化銅粒子。又，粒徑不及200奈米之氧化亞銅的合成方， 法’已知有乙醯丙酮根銅錯合物在聚醇溶劑中於約20(TC加 熱合成之方法（Angewandt Chemie Internation Edtiion， Νο·40，vo 1·2 ’ Ρ·359.2001)，有機銅化合物（銅-N-亞硝基苯 基羥胺錯合物）於十六胺等保護劑存在下，在鈍性環境氣體 中，於約 3 00°C之高溫加熱的方法（J.Am.Chem.Soc.，1999 ，vol. 121，p. 1 1 5 95)。 經濟部智慧財產局員工消費合作社印製 又，用於本發明之金屬氧化物粒徑在200奈米以下， 僅須加熱處理時無妨於粒子間之熔合，金屬氧化物粒子之 一部份亦能用可還原之金屬氧化物以外之材料取代。可還 原之金屬氧化物以外之材料，有例如金屬，以500°C以下之 加熱不還原之金屬氧化物，或有機化合物，中心部份係金 屬，表面以金屬氧化物覆蓋之芯-殼型金屬-金屬氧化物複合 微粒即係一例。 用於本發明之金屬氧化物微粒，在金屬氧化物分散體 中互相微弱凝集亦無妨，以網印塗布時可於印刷前再分散 使凝集體不堵塞網目者爲較佳。又，在噴墨塗布之用途 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -12- 1236931 經濟部智慧財產局員工消費合作社印製 A7 _ _B7___五、發明説明（9 ) •中，凝集體之粒徑以不及1 00奈米爲佳。此等凝集體可係 二次凝集體，其粒徑可藉雷射散射法測出。 金屬氧化物之重量占金屬氧化物分散體總重量之5重 量％以上95重量％以下，10重量％以上80重量％以下爲較 佳。不及5重量％時，單次的塗布•煅燒所得金屬薄膜厚度 低，而超過95重量％時，分散體粘度過高，有難以塗布於 基材上之問題。 用於本發明之分散媒體係有機溶劑及/或水’有機分 散媒體之例，有液態之醇系溶劑、酮系溶劑、醯胺系溶劑 、酯系溶劑及醚系溶劑。 在此，醇系溶劑有甲醇、乙醇、正丙醇、異丙醇、正 丁醇、異丁醇、二級丁醇、三級丁醇、正戊醇、異戊醇、 2-甲基丁醇、二級戊醇、三級戊醇、3-甲氧基丁醇、正己醇 、2-甲基戊醇、二級己醇、2-乙基丁醇、二級庚醇、庚醇_3 、正辛醇、2-乙基己醇、二級辛醇、正壬醇、2，6-二甲基 庚醇-4、正癸醇、二級十一醇、三甲基壬醇、二級十四醇 、二級十七醇、酚、環己醇、甲基環己醇、3，3，5 -三甲基 環己醇、苯甲醇、二丙酮醇等單醇溶劑，及乙二醇、1 ’ 2-丙二醇' 1，3-丁二醇、戊二醇-2，4、2-甲基戊二醇-2，4、 己二醇-2，5、庚二醇-2，4、2-乙基己二醇-1，3、二乙二醇 、二丙二醇、.己二醇、辛二醇、三乙二醇、三丙二醇、甘 油等多元醇溶劑，及乙二醇單甲醚、乙二醇單***、乙二 醇單丙醚、乙二醇單丁醚、乙二醇單己醚、乙二醇單苯醚 、乙二醇單h乙基丁醚、二乙二醇單甲醚、二乙二醇單乙 本紙張尺度適用中國國家標準（CNS ) A4規格（210 X297公釐） (請先閲讀背面之注意事項再填寫本頁) -13- 1236931 A7 ___ B7_ 五、發明説明（10) 醚、二乙二醇單丙醚、二乙二醇單丁醚、二乙二醇單己醚 (請先閱讀背面之注意事項再填寫本頁) .、丙二醇單甲醚、丙二醇單***、丙二醇單丙醚、丙二醇 單丁醚、二丙二醇單甲醚、二丙二醇單***、二丙二醇單 丙醚等多元醇部份醚溶劑等。此等醇系溶劑可1種或2種 以上同時使用。 酮系溶劑有丙酮、丁酮、甲基正丙基酮、甲基正丁基 酮、二乙基酮、甲基異丁基酮、甲基正戊基酮、乙基正丁 基酮、甲基正己基酮、二異丁基酮、三甲基壬酮、環己酮 、2-環己酮、甲基環己酮、2，4 -戊二酮、丙酮基丙酮、甲 基苯基酮，以及乙醯丙酮、2，4 -己二醇、2，4·庚二酮、3 ，5 -庚二酮、2，4 -辛二酮、3，5 -辛二酮、2，4 -壬二醇、3 ’ ，5-壬二酮、5-甲基-2，4-己二酮、2，2，6，6-四甲基-3, 5-庚二酮、1，1，1，5，5，5-六氟-2，4-庚二酮等 /3-二酮 類等。 經濟部智慧財產局員工消費合作社印製 醯胺系溶劑有甲醯胺、N-甲基甲醯胺、N，N-二甲基甲 醯胺、N -乙基甲醯胺、N，N -二乙基甲醯胺、乙醯胺、N -甲 基乙醯胺、N，N-二甲基乙醯胺、N-乙基乙醯胺、N，N-二 乙基乙醯胺、N-甲基丙醯胺、N-甲基吡咯烷酮、N-甲醯基 嗎啉、N-甲醯基哌啶、N-甲醯基吡咯烷、N-乙醯基嗎啉、 N-乙醯基哌啶、N-乙醯基吡咯烷等。 I 酯系溶劑有碳酸二乙酯、碳酸乙烯酯、碳酸丙烯酯、 碳酸二乙酯、醋酸甲酯、醋酸乙酯、T -丁內酯、r -戊內酯 、醋酸正丙酯、醋酸異丙酯、醋酸正丁酯、醋酸異丁酯、 醋酸二級丁酯、醋酸正戊酯、醋酸二級戊酯、醋酸3 -甲氧 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -14 - 1236931 A7 B7 五、發明説明（11) (請先閲讀背面之注意事項再填寫本頁) ' 基丁酯、醋酸甲基戊酯、醋酸2-乙基丁酯、醋酸2-乙基己 酉旨、醋酸苯甲酯、醋酸環己酯、醋酸甲基環己酯、醋酸正 壬酯、乙醯醋酸甲酯、乙醯醋酸乙酯、醋酸乙二醇單甲醚 酯、醋酸乙二醇單***酯、醋酸二乙二醇單甲醚酯、醋酸 二乙二醇單***酯、醋酸二乙二醇單正丁醚酯、醋酸丙二 醇單甲醚酯、醋酸丙二醇單乙酯、醋酸丙二醇單丙醚酯 、醋酸丙二醇單丁醚酯、醋酸二丙二醇單甲醚酯、醋酸二 丙二醇單***酯、乙二酯二醋酸酯、甲氧基三甘醇酯酸酯 、丙酸乙酯、丙酸正丁酯、丙酸異戊酯、單酸二乙酯、草 _ 酸二正丁酯、乳酸甲酯、乳酸乙酯、乳酸正丁酯、乳酸正 戊酯、丙二酸二乙酯、酞酸二甲酯、酞酸二乙酯等。此等 酯系溶劑可以1種或2種以上同時使用。 醚系溶劑有二丙醚、二異丙醚、二噚烷、四氫呋喃、 四氫吡喃、乙二醇二甲醚、乙二醇二***、乙二醇二丙醚 、丙二醇二甲醚、丙二醇二*** '丙二醇二丙醚、二乙二 醇二甲醚、二乙二醇二***、二乙二醇二丙醚等。 經濟部智慧財產局員工消費合作社印製 此等分散媒體可單獨使用，亦可混合2種以上之分散 媒體使用。尤以在噴墨塗布用途，可均勻分散粒徑不及200 奈米之金屬氧化物，且金屬氧化物分散體粘度可降低者爲 • 佳。 本發明之金屬氧化物分散體，須於分散媒體含多元醇 及/或聚醚化合物。多元醇、聚醚化合物可係固體或液體 。含於金屬氧化物分散體之多元醇、聚酯化合物係固體時 ，可溶解於上述有機溶劑及/或水分散媒體使用。另一方 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐) — -15- 1236931 A7 B7 ，五、發明説明（12) 面’含於金屬氧化物分散體之多元醇、聚醚化合物係液體 時’其本身即具分散媒體之作用。 (請先閱讀背面之注意事項再填寫本頁) 本發明中，多元醇者指具2以上羥基之化合物。又， 聚醚化合物亦指具2以上醚結合之化合物。在此，兼具2 以上之羥基及醚結合之化合物，依以下標準分類爲其一；（i) 經基數（下稱nl)多於醚結合數（下稱n2)時（nl>n2)之化合物 物歸類爲多元醇，（丨丨）而nl<n2或ni = n2時，烯類爲聚醚化 合物。例如，麥芽三糖係一種三糖類，分子骨架中有11個 羥基，5個醚結合，依上述標準，歸類爲多元醇。又，三甘 醇因分子骨架中，羥基及醚結合各2，依上述標準歸類爲聚 醚化合物。 經濟部智慧財產局員工消費合作社印製 金屬氧化物分散體中含多元醇時即可提升金屬氧化物 粒子之分散性。多元醇有例如乙二醇、二乙二醇、1，2 -丙 二醇、1，3-丙二醇、1，2-丁 二醇、1，3-丁 二醇、1，4-丁 二醇、2 -丁烯-1，4-二醇、2，3-丁二醇、戊二醇、己二醇 、辛二醇、1，1，1-三羥甲基乙烷、2-乙基-2-羥甲基-1，3-丙二醇、1，2’ 6-己三醇、1，2，3 -己三醇、1，2，4-丁三 醇等。又’亦可使用甘油、蘇糖醇、赤蘚醇、季戊四醇、 .戊五醇、己糖醇等糖醇、戊五醇含木糖醇、核糖醇、阿糖 醇。又’己糖醇包含甘露糖醇、山梨糖醇、甜醇等。又， 亦可使用甘油醛、二羥基丙酮、蘇糖、赤蘚酮糖、赤蘚糖 、阿糖、核糖、核酮糖、木糖、木酮糖、來蘇糖、葡萄糖 、果糖、甘露糖、艾杜糖、山梨糖、古羅糖、塔羅糖、塔 格糖、半乳糖、阿洛糖、阿卓糖、乳糖、異麥芽糖、葡庚 本紙張尺度適用中國國家標準（CNS ) A4規格（210 X297公釐） -16- 1236931 A7 —B7 五、發明説明（I3) 糖、庚糖、麥芽二糖、萵苣二糖、海藻糖等糖類。此等多 元醇因具還原性，於金屬氧化物還原之際有利。 (請先閲讀背面之注意事項再填寫本頁) 特佳之多元醇係碳原子數10以下之多元醇，其中液狀 而粘度低者如上述其本身具分散媒體之作用故爲較佳。如 此之多元醇有例如乙二醇、二乙二醇、1，2-丙二醇、1，3-丙二醇、1，2 -丁 二醇、1，3 -丁 二醇、1，4 -丁 二醇、2，3-丁二醇、戊二醇、己二醇、辛二醇等。 ' 多元醇中尤以甘油、蘇糖醇、赤蘚醇、季戊四醇、戊 五醇、己糖醇等糖醇類，因尤有利於提升金屬氧化物分散 體中之金屬氧化物微粒之抗凝集性故係更佳。 多元醇之較佳添加量係占金屬氧化物分散體之總重量 0.1重量％以上95重量％以下，1重量％以上90重量％以 下更佳。不及〇. 1重量％時，金屬氧化物粒子分散性提升 效果小，若超過9 5重量％，則分散體中金屬氧化物之量 少，難以形成優質金屬薄膜故不佳。此等多元醇可單獨使 用，亦可混合多數之多元醇使用。 經濟部智慧財產局員工消費合作社印製 金屬氧化物分散體中含聚醚化合物，該分散體煅燒所 得之金屬薄膜緻密性即可提升，且與基材之粘合性提升。 聚醚化合物係骨架中有醚結合之化合物，以均勻分散於分 散媒體爲佳。又，隨金屬氧化物分散體之是否含聚醚化合 物，利用該金屬氧化物分散體所得之金屬薄膜的微觀結構 不同。金屬氧化物分散體中聚醚化合物之含量占金屬氧化 物分散體總重量不及〇· 1重量％時，所得金屬薄膜係具孔徑 1微米以下之多孔結構的多孔性金屬薄膜。另一方面，金屬 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） 一 " -17- 1236931 A7 _B7__ 五、發明説明（Μ) 氧化物分散體中聚醚化合物含量占金屬氧化物分散體總重 量在0.1至70重量％以下時，所得金屬薄膜極少有孔’且 其孔徑小，因此，緻密性更加提升。 於金屬氧化物分散體加入聚醚化合物，煅燒而得之金 屬薄膜之緻密性及粘合性提升之理由雖不確實，但應係煅 ' 燒時可防金屬氧化物微粒間之局部造粒，且極少量之聚醚 化合物，直接或經碳之還原而殘留於作爲粘結劑之金屬薄 膜中，或與基材的界面之故。 聚醚化合物以易受金屬氧化物還原得之金屬分解，尤 以在有氫等還有氣體存在之環境氣體中易起低溫催化分解 ，容易消失者爲佳。聚醚化合物因本身具還原性，於金屬 氧化物還原之際有利。 聚醚化合物從金屬氧化物微粒往分散媒體中之分散性 的觀點，係以非晶性聚醚化合物爲佳，尤以重複單元係碳 、原子數2至8之直鏈或環狀氧化烯基之脂族聚醚爲佳。重 複單元係碳原子數2至8之直鏈或環狀烯基之脂族聚醚的 分子結構可係環狀、直鏈、或分枝狀，亦可係2元以上之 聚醚共聚物或2元以上之聚醚嵌段共聚物。具體而言，有 聚乙二醇、聚丙二醇、聚丁二醇等之聚醚單聚物，乙二醇/ 丙二醇、乙二醇/丁二醇之2元共聚物，乙二醇/丙二醇/乙 二醇、丙二醇/乙二醇/丙二醇、乙二醇/丁二醇/乙二醇等直 鏈3元共聚物，但不限於此等。嵌段共聚物有聚乙二醇聚 丙二醇、聚乙二醇聚丁二醇等之2元嵌段共聚物，以及聚 乙二醇聚丙二醇聚乙二醇、聚丙二醇聚乙二醇聚丙二醇、 本紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ297公釐） (請先閱讀背面之注意事項再填寫本頁) 裝- 訂 經濟部智慧財產局員工消費合作社印製 -18- 1236931 A7 ____B7_ 五、發明説明（15) 聚乙二醇聚丁二醇聚乙二醇等直鏈3元嵌段共聚物等之聚 醚嵌段共聚物。 (請先閲讀背面之注意事項再填寫本頁} 用於本發明之聚醚化合物亦可於分子結構中含其它官 .能基’例如醇基、酯基、環氧丙基、亞胺基、烷基、醯胺 基、胺基、苯基、醛基、碳酸基、異氰酸酯基、磺醯基等 ’或組合此等基而構成，含烷基酯基、烷基醯胺基及烷基 碳酸酯基等取代基，但不限於此。亦包含可聚合之乙烯基 、偏乙烯基、亞乙烯基、環氧丙基、烯丙基，及含此等基 之丙烯酸酯基、甲基丙烯酸酯基。此等官能基可於分子中 有多數個，例如糖，或於分子中含糖醇等多元醇亦可。 經濟部智慧財產局員工消費合作社印製 含於糖醇之羥基結合有聚合物鏈之結構，係於甘油、 蘇糖醇、赤蘚醇、季戊四醇、戊五醇、己糖醇等所含之羥 基結合聚合物鏈，其例有甘油聚乙二醇聚丙二醇、赤蘚醇 •聚乙二醇聚丙二醇聚乙二醇等。糖鏈之具體例有甘油醛、 二羥基丙酮、蘇糖、赤蘚酮醇、赤蘚糖、阿糖、核糖、核 酮糖、木糖、木酮糖、來蘇糖、葡萄糖、果糖、甘露糖、 艾杜糖、山梨糖、古羅糖、塔羅糖、塔格糖、半乳糖、阿 洛糖、阿卓糖、乳糖、異麥芽糖、葡庚糖、庚糖、麥芽三 糖、萵苣三糖、海藻糖等。 又，用於本發明之脂族聚醚，其末端基無特殊限制。 末端基有經羥基、碳原子數1至8之直鏈、分枝或環狀烷 基醚基，烷基酯基、烷基醯胺基、烷基碳酸酯基、氨酯基 或三烷基矽烷基等改質者等。以下列出脂族聚醚之末端基 '改質之具體例。 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -19- 1236931 A7 ____ B7 五、發明説明（16) (請先閱讀背面之注意事項再填寫本頁) 至少一末端烷基醚化之例有以甲醚、***、丙醚、環 氧丙醚等醚化者，具體例有聚乙二醇單甲醚、聚乙二醇二 甲醚、聚丙二醇二甲醚、聚異丁二醇二甲醚、聚乙二醇二 ***、聚乙二醇單***、聚乙二醇二丁醚、聚乙二醇單丁 醚、聚乙二醇二環氧丙醚、聚乙烯聚丙二醇二甲醚、甘油 聚乙二_二甲醚、季戊四醇聚乙二醇四甲醚、戊五醇聚乙 二醇五甲醚、山梨糖醇聚乙二醇六甲醚等。 末知有酯基之脂族聚旨迷類有，至少一末端成爲例如醋 酸酯、丙酸酯、丙烯酸酯、甲基丙烯酸酯、苯甲酸酯者。 烯二醇類末端羧基甲醚化，該末端化之羧基烷基酯化者亦 適用。較佳具體例有聚乙二醇單醋酸酯、聚乙二醇二醋酸 酯、聚丙二醇單醋酸酯、聚丙二醇二醋酸酯、聚乙二醇二 苯甲酸酯、聚乙二醇二丙烯酸酯、聚乙二醇單甲基丙烯酸 酯、聚乙二醇二甲基丙烯酸酯、聚乙二醇雙羧基甲醚二甲 酯、聚丙二醇雙羧基甲醚二甲酯、甘油聚乙二醇三醋酸酯 、季戊四醇聚乙二醇四醋酸酯、戊五醇聚乙二醇五醋酸酯 、山梨糖醇聚乙二醇六醋酸酯等。 經濟部智慧財產局員工消費合作社印製 末端有醯胺基之脂族聚醚類，係至少一末端羧基甲醚 化，然後醯胺化，或羥基末端之胺基改質後醯胺化者等， 適用者具體有，聚乙二醇雙（羧基甲醚二甲基醯胺）、聚丙二 ，醇雙（羧基甲醚二甲基醯胺）、聚乙二醇雙（羧基甲醚二乙基 醯胺）、甘油聚乙二醇三羧基甲醚二甲基醯胺、季戊四醇聚 乙二醇四羧基甲醚二甲基醯胺、戊五醇聚乙二醇五羧基甲 醚二甲基醯胺、山梨糖醇聚乙二醇六羧基甲醚二甲基醯胺 本纸張尺度適用中國國家標準（CNS ) A4規格（210X29<7公釐） 1236931 A7 ______ B7 五、發明説明（17) 等。 (請先閱讀背面之注意事項再填寫本頁) 末端有烷基碳酸酯基之脂族聚醚類，有例如上述烯二 醇類之至少一末端附加以甲醯酯基者，具體有雙甲氧基羰 基氧基聚乙二醇、雙乙氧基羰基氧基聚乙二醇、雙乙氧基 鑛基氧基聚丙二醇、雙三級丁氧基羰基氧基聚乙二醇等。 亦可使用末端以氨酯基、三烷基矽烷基改質之脂族聚 醚類。三烷基矽烷基改質係以三甲基矽烷基改質爲尤佳， 此可藉三甲基氯矽烷、三甲基氯矽烷基乙醯醯胺或六甲基 二矽氨烷等改質。 從分散媒體中之溶解度及金屬氧化物的分散性之觀點 ’脂族聚醚之最佳末端基係羥基·聚醚化合物中之低分子量 液態物，其本身可用作分散媒體。 經濟部智慧財產局員工消費合作社印製 爲煅燒含聚醚化合物之金屬氧化物分散體得高導電性 .之金屬薄膜，聚醚化合物係以可經低溫煅燒即焚化者爲佳 ，分子量以150至6000爲佳，250至1 500爲更佳。所用聚 醚化合物分子量過大者锻燒時不易焚化，殘存於金屬薄膜 中之聚醚化合物的量大。金屬薄膜中聚醚化合物殘留量大 時，會有金屬薄膜的體積電阻値高之問題。而聚醚化合物 之分子量過大時，於分散媒體之分散性不足而不佳。另一 方面，分子量若過小，則加熱處理之金屬薄膜成膜性及緻 密性低而不佳.。 金屬氧化物分散體中聚醚化合物之添加量，係占金屬 氧化物分散體總重量0.1至70重量％，1至50重量％爲更 •佳。聚醚化合物之添加量不及〇 · 1重量％時，還原自金屬氧 本紙張尺度適用中國國家標準（CNS)A4規格（210X 2叼公釐） -21- 1236931 A7 __B7 五、發明説明（18) 化物之金屬，粒子間緻密性低，並有與基材之密合性下降 之傾向。另一方面，聚醚化合物添加量超過7〇重量％時， (請先閱讀背面之注意事項再填寫本頁) •金屬氧化物分散體之粘度有上升之傾向而不佳。 將金屬氧化物分散於分散媒體之方法，可用一般分散 粉體於液體之方法。例如，超音波法、混合機法、三輕法 、二輥法、立式球磨機、斑伯里混合機、漆料振動機、捏 合機、均質機、球磨機、沙磨機等。通常係組合多數之此 等分散手段進行分散。多元醇（及/或聚醚化合物）係液態時 ’可將多兀醇（及/或聚醚化合物）及金屬氧化物加入於分散 媒體，同時分散處理。另一方面，多元醇及/或聚醚化合 物）係固態時’以將多元醇（及/或聚醚化合物）溶解於分散 媒體後，加入金屬氧化物於所得溶液，作分散處理爲佳。 此等分散處理可於室溫進行，爲降低溶劑粘度，亦可於加 熱下爲之。於本發明所用之分散媒體中合成粒徑不及2〇〇 奈米之金屬氧化物，可省略金屬氧化物之分散處理。 金屬氧化物分散體用之分散媒體，特佳者爲碳原子數 10以下之多元醇，且於分散媒體中含上述聚醚化合物者。 經濟部智慈財產局員工消費合作社印製 使金屬氧化物分散體中含金屬氧化物粒子以外之金屬 粉，可改善加熱處理所得金屬接合層之特性，同時，減少 金屬氧化物微粒用量故較佳。可用之金屬粉無特殊限制， 有例如金、銀、銅、鈀、鉑、鎳、鉻、鋁、錫、鋅、鈦、 . 鎢、鉅、鋇、铑、釕、餓、鉍、銥、鈷、銦、鐵、鉛等， 可隨目的選用1種或多種金屬粉。爲求高導電性時，以用 工業上可廉價取得之銀、鎳、銅等特佳。銀因可賦予金屬 本紙張尺度適用中國國家標準（CNS ) A4規格（210 X 297公釐） -22 - 1236931 A7 _B7____ 五、發明説明（θ 薄膜高抗氧化性故較佳。又，有抗遷移性之必要時’可& 金屬接合層多加抗遷移性強之銅粉。 (請先閱讀背面之注意事項存填寫本頁) 此等金屬粉之粒徑無特殊限制，宜隨目的使用較佳粒 徑之金屬粉。以煅燒得金屬薄膜時，金屬粉粒徑以100微 米以下爲佳，10微米以下更佳。金屬粉粒徑在100微米以 上時，金屬粉與金屬氧化物微粒尺寸相差過大，金屬接合 層之平滑性下降而不佳。金屬氧化物分散體在用於噴墨用 墨料時，金屬粉粒徑係以200奈米以下爲佳，100奈米以下 更佳。 加於金屬氧化物分散體之金屬粉，其量係以該金屬粉 與金屬氧化物微粒含量合計，占金屬氧化物分散體總重量5 重量％以上9 5重量％以下爲佳。金屬粉與金屬氧化物微粒 之重量比，以9:1至1:9爲佳。金屬粉及金屬氧化物微 粒含量不及5重量％時添加效果小，若超過95重量％則金 .屬氧化物分散體之粘度上升，分散體之塗布、充塡困難而 不佳。金屬粉與金屬氧化物微粒之重量比超出9: 1至1: 9 之範圍時，二種粒子之混合效果變小而不佳。 經濟部智慧財產局員工消費合作社印製 於上述金屬氧化物分散體中添加熱固性樹脂，經加熱 硬化提升與金屬面之粘合性，並提升強度故較佳。可用之 熱固性樹脂須可溶於所用分散媒體，並無損於金屬氧化物 分散體之分散性，此外無特殊限制。有例如環氧樹脂、酣 樹脂、淸漆樹脂、聚醯亞胺樹脂、聚氨酯、三聚氰胺樹脂 、尿素樹脂等。 環氧樹脂有例如雙酚Α型環氧樹脂、雙酚F型環氧樹 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） " —~~一 - -23- 1236931 A7 B7 五、發明説明（20) (請先閱讀背面之注意事項再填寫本頁) 脂、（甲酚）淸漆型環氧樹脂、鹵化雙酚型樹脂、間苯二酚型 、四羥基酚乙烷型、聚醇聚二醇型、甘油三醚型、聚烯烴 型、環氧化大豆油、環戊二烯二氧化物、乙烯環己烯二氧 化物等。 液態環氧樹脂因粘度低而較佳，其例有苯氧基烷基單 環氧丙醚、雙酚A二環氧丙醚、丙二醇二環氧丙醚、丙二 醇二環氧丙醚、己二醇二環氧丙醚、加氫雙酚A二環氧丙 ‘醚、新戊二醇二環氧丙醚、甘油二環氧丙醚、N，N-二環氧 丙基苯胺、N，N-二環氧丙基甲苯胺、三羥甲基丙烷三環氧 丙醚、甘油三環氧丙醚及各種液態聚矽氧烷二環氧丙醚等 〇 液態環氧樹脂中，以可良好分散於多元醇分散媒體之 醇型環氧樹脂爲較佳，有例如聚乙二醇二環氧丙醚、聚丙 二醇二環氧丙醚、1，4-丁二醇二環氧丙醚等。 經濟部智慧財產局員工消費合作社印製 用於本發明之環氧樹脂硬化劑可係一般的環氧硬化劑 。有例如脂族多胺系之三乙四胺、間二甲苯二胺等，芳族 胺系之間苯二胺、二胺基二苯硕等，三級胺系有苯甲基二 甲胺、二甲胺基甲基酚等，酸酐系有酞酸酐、六氫酞酐等 ，三氟硼胺錯合物系有BF3-哌啶錯合物等。又，雙酚A等 雙酚化合物亦可。二醯胺、2-乙基-4-甲基咪唑、參（甲胺基 )矽烷等亦可使用。樹脂系硬化劑有，亞麻酸二聚物與乙二 胺等製成之聚醯胺樹脂，兩端有毓基之聚硫醚樹脂、淸漆 系酚樹脂等。此等可單獨使用，亦可組合2種以上使用。 硬化劑之添加量隨硬化劑之種類而異，例如酸酐系等 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -24- 1236931 A7 __ _ B7 五、發明説明（21) (請先閱讀背面之注意事項再填寫本頁) 依化學計量與環氧丙基反應時，係由環氧當量決定最適添 加量。觸媒反應時一般係3至30重量°/。。此時硬化劑之室 溫反應性高時’可於使用前隨即將含啓始劑之液體混入粘 合劑’或將硬化劑封入1 00微米左右之明膠等的囊胞製成 微囊等。 熱固性樹脂之其它例聚醯亞胺樹脂，係其前驅物聚醯 •胺酸溶液經加熱縮合而得，可用於本發明之聚醯胺酸，可 由四羧酸二酐與二胺基化合物製造。四羧酸二酐之例有苯 均四酸二酐、3,3>，4,4,-二苯基酮四羧酸二酐、l，4,5,8-萘 四羧酸二酐、2,3,6,7-萘四羧酸二酐、1，2,5,6，-萘四羧酸二酐 、3,3 /，4,4 / -聯苯四羧酸二酐、2,2 /，3,3 / -聯苯四羧酸二 酐、2,3,3 —，4聯苯四羧酸二酐、2,3,3 >，4 〃 -二苯基酮四 羧酸二酐、2,2-雙（3,4-二羧基苯基）丙烷二酐、2,2-雙[5-(3， 心二羧基苯氧基）苯基]丙烷二酐等、二胺基化合物有例如間 苯二胺、對苯二胺、2,4-甲苯二胺、3,3二胺基二苯醚、3 ，4 '二胺基二苯醚、4,4 '二胺基二苯醚、3,3 '二胺基 一本硕、4,4 -一胺基一苯硕、3,4 -二胺基二苯硕、3， 經濟部智慧財產局員工消費合作社印製 3一-二胺基二苯甲烷、4,4>-二胺基二苯基甲烷、3, 4，-二 胺基二苯基甲烷、4，4> -二胺基二苯亞碾、3，3 —-二胺基二 苯基酮、4〆/-二胺基二苯基酮、3，4，-二胺基二苯基酮、2 ，2 / -雙（4-胺基苯基）丙烷等。 本發明中，於金屬氧化物分散體之熱固性樹脂的添加 量，以占分散媒體、聚醚化合物及該熱固性樹脂總重量0.1 至20重量％爲佳，1至10重量％爲更佳。熱固性樹脂量不 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐〉 -25- 1236931 A7 __ B7_ 五、發明説明（22) 及0· 1重量％時添加效果小，而若超過20重量％則因金屬 接合層之導電性顯著下降，不適作金屬薄膜形成材料。 (請先閱讀背面之注意事項再填寫本頁) 本發明中，多元醇及聚醚化合物具還原性，有還原金 屬氧化物之效果，而除多元醇及聚醚化合物以外，更於金 屬氧化物分散體中添加可還原金屬氧化物之還原劑，能使 金屬氧化物更易於還原而爲較佳。此時，僅須能還原金屬 >氧化物，可用之還原劑無特殊限制，無機還原劑，有機還 原劑均可。無機還原劑有例如硼氫化鈉、硼氫化鋰等氫化 合物，二氧化硫等硫化合物，亞硫酸鹽等低級氧化物之鹽 ，碘化氫、碳等。 多元醇、聚醚化合物以外之有機還原劑有例如，醛類 、肼、二亞胺類、草酸等。醛類有例如甲醛、乙醛、丙醛 、丁醛、異丁醛、戊醛、異戊醛、三甲基乙醛、己醛、庚 酉签、辛酸、壬酸、--醒、月桂酸、十三醒、肉豆蔻醛、 經濟部智慧財產局員工消費合作社印製 十五醛、棕櫚醛、十七醛、硬脂醛等脂族飽和醛、乙二醛 、琥珀醛等脂族二醛、丙烯醛、巴豆醛、丙炔醛等脂族不 • 飽和醛、苯甲醛、鄰甲苯醛、間甲苯醛、對甲苯醛、水楊 醛、肉桂醛、α -萘醛、/3 -萘醛等芳族醛，糠醛等雜環 醛等。 二亞胺類係例如由偶氮二羧酸鹽、羥胺-0 -磺酸、Ν -丙 二烯磺醯肼或Ν-醯基磺醯肼熱分解而得。Ν-丙二烯磺醯肼 或Ν-醯基磺醯胼有例如，對甲苯磺醯肼、苯磺醯肼、2,4,6-參異丙基苯磺醯胼、氯乙醯肼、鄰硝基苯磺醯肼、間硝基 苯磺醯肼、對硝基苯磺醯肼等。 本紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ297公釐〉 -26 - 1236931 經濟部智慧財產局員工消費合作社印製 A7 B7 ____五、發明説明（2》 多元醇及聚醚化合物以外的還原劑之含量，係占金屬 氧化物分散體總重量〇. 1至70重量°/。，以0.1至50重量％ 爲佳，0 · 1至2 0重量％爲更佳，1至1 0重量％又更佳。 本發明中，爲提升煅燒得之金屬薄膜的強度及與基材 之粘合性，亦可於金屬氧化物分散體中添加金屬氧化物等 . 金屬氧化物前驅物。金屬氧化物如一般式M(〇V)n，其中Μ 係金屬元素。R1係院基，η係金屬元素之氧化數。Μ有如石夕 、欽、銷、銘等，院基有例如甲基、乙基、異丙基、正丁 基、三級丁基等，代表性金屬氧化物有四甲氧基矽烷、四 乙氧基矽烷、四（正丙氧基）矽烷、四（異丙氧基）矽烷、四（ 正丁氧基）矽烷、四（二級丁氧基）矽烷、四（三級丁氧基）矽 烷等之矽化合物，四乙氧基鈦、四（正丙氧基）鈦、四（異丙 氧基）鈦、四（正丁氧基）鈦、四（二級丁氧基）鈦、四（三級丁 氧基）鈦等鈦化合物等，此等化合物係液態，容易分散於金 屬氧化物分散體故而較佳。又，亦可使用 • 在1以上）所表之金屬烷氧化物，其金 屬直接附加以有機基R2。有機基R2有例如曱基、乙基、丙 基、苯基、丁基等。 將金屬粉、熱固性樹脂、還原劑、金屬烷氧化物等材 料分散於金屬氧化物分散體之方法，可係超音波法、混合 機法、二輥法、一輥法、立式球磨機、斑伯里混合機、漆 料振動機、捏合機、均質機、球磨機、沙磨機法等一般方 法。此等之分散亦可與金屬氧化物與多元醇（及/或聚醚化 合物）之分散於分散媒體同時進行。 本紙適用中國國家標準（CNS ) A4規格（210 X 297公釐） — 一 -27- (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局Μ工消費合作社印製 1236931 ' A7 _____ B7 五、發明説明（ 其次說明，使用本發明之金屬氧化物分散體，於基板 上形成金屬薄膜之方法（形成基板及金屬薄膜所成層合體之 方法）。 基板可用無機或有機基板。無機基板可用玻璃基板， 石夕、鍺等半導體基板，鎵-砷、銦-銻等化合物半導體基板等 ’此等之表面亦可先形成其它物質之薄膜後使用。此時之 溥膜可係銘、欽、鉻、鎳、銅、銀、組、鎢、餓、銷、金 •等金屬’二氧化矽、氟化玻璃、磷玻璃、硼磷玻璃、硼矽 酸玻璃、多晶砂、氧化鋁、氧化鈦、氧化錯、氮化砂、氮 化鈦、氮化鉅、氮化硼、氫化倍半氧烷、ITO (銦錫氧化物） 等無機化合物，甲基倍半氧烷、非晶碳、氟化非晶碳、聚 醯亞胺等所成之薄膜。 有機基板若在金屬氧化物分散體之加熱處理溫度不受 熱之損傷者即無限制，可用例如聚醯亞胺基板、聚對酞酸 乙二醇酯（PET)基板、芳族聚醯胺基板、環氧基板、含氟樹 脂基板等。 形成金屬薄膜前，爲提升密合性等，可先用電漿處理 、電子束處理等物理手法作處理，亦可用密合促進劑等之 化學手法作處理。密合促進劑可用所謂的矽烷偶合劑、ί呂 螯合物等。較佳者有3-胺基丙基三甲氧基矽烷、3-胺基丙 基三乙氧基矽烷、Ν(2-胺基乙基）-3-胺基丙基三甲氧基矽院 、N-( 2-胺基乙基）-3-胺基丙基甲基二甲氧基矽烷、乙烯基三 氯矽烷、乙烯基三乙氧基矽烷、3-氯丙基三甲氧基矽烷、 氯丙基甲基二氯矽烷、3-氯丙基甲基二甲氧基矽烷、3_氯丙 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） (請先閱讀背面之注意事項再填寫本頁)1,1T Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 1236931 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 _ B7 ____. V. Description of the invention (6)% by weight or less. i 6. The metal oxide dispersion according to any one of the above items 1 to 15, wherein the content of the polyether compound is 0.1 to 70% by weight based on the total weight of the metal oxide dispersion. 17. The metal oxide dispersion of any one of the above items 1 to 15, wherein the content of the polyether compound accounts for less than 0.1% by weight of the total weight of the metal oxide dispersion. 〇1 8 · Calcination of the metal oxide of the above item 16 Most of the metal particles with a primary particle size of less than 200 nanometers are obtained from the dispersion, and the gold * formed by fusing the contact parts is a thin film. 19. The metal oxide dispersion of item 17 above is obtained by calcination. Most of the metal particles with a primary particle diameter less than 2000 nanometers agglomerate, and the metal film with a porous structure formed by the contact part fusion. 20. A method for producing a metal thin film comprising applying the metal oxide dispersion of any one of the above items 1 to 16 to a substrate and applying heat treatment thereto. 2 1. The method of manufacturing a metal thin film according to item 20 above, which comprises performing a heat treatment in a non-oxidizing ambient gas. 22. The method of manufacturing a metal thin film according to item 20 above, comprising coating the substrate with a metal oxide dispersion, heating and calcining in a passive ambient gas, and then heating and calcining in a reducing ambient gas. 23. The method for producing a metal thin film according to any one of items 20 to 22 above, wherein the heat treatment temperature is 50 ° C to 500 ° C. The best embodiment of the invention The paper size applies the Chinese National Standard (CNS) A4 specification (210 ' < 297 公 ^] --------- -10- (Please read the notes on the back before filling out this page) 1236931 Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Invention Description (7 ). The present invention is described in detail below. As described above, the metal oxide dispersion of the present invention includes essential components such as a metal oxide having a particle size of less than 200 nm, and a dispersion medium. The metal oxide dispersion of the present invention is characterized in that the dispersion medium contains a polyol and / or a polyether compound. These components are described below. The metal oxide used in the present invention has a particle diameter of less than 200 nm, more preferably less than 100 nm, and more preferably less than 30 nm. Here, the particle diameter refers to a primary particle diameter, and can be measured by morphological observation using an electron microscope or the like. When the particle size is less than 200 nanometers, the metal particles reduced due to metal oxides are small, the surface energy becomes large, and the melting point decreases. The metal particles should be fused at low temperature to form a thin metal film. The smaller the metal oxide particle size, the easier the reduction of the metal oxide particles, so from the viewpoint of ease of reduction, the smaller the metal oxide particles, the better. When the particle diameter of the metal oxide is more than 200 nm, the fusion between the metal particles obtained by the reduction treatment is insufficient, and a dense and strong structure must not be formed. On the other hand, when the particle size is less than 100 nanometers, it can be used as a conductive ink for the inkjet method for extruding tiny droplets to form fine wiring. It is suitable for the formation of fine circuits without etching treatment. Anyone that can be reduced by heat treatment can be used. Each metal oxide particle may be composed of a single metal oxide, and a composite metal oxide composed of a plurality of metal oxides is also preferable. The volume resistance of a metal obtained by reducing a metal oxide is preferably less than lx 10 "ohm centimeters, and more preferably less than lx 10 · 5 ohm centimeters. The use of such metal oxides is preferred because the resulting metal thin film has high conductivity. .Such metal oxides are, for example, silver oxide, copper oxide, palladium oxide, nickel oxide, lead oxide, cobalt oxide, etc. Among them, the Chinese National Standard (CNS) A4 specification (210X297 mm) is applicable due to the paper scale (please first Read the precautions on the back and fill out this page) -11-1236931 A7 B7 V. Description of the invention (8) (Please read the precautions on the back before filling out this page) Easy reduction and high conductivity after reduction, with copper oxide and oxidation Silver is particularly preferred. Silver oxides include the first silver oxide, the second silver oxide, and the third silver oxide. The oxidation state of silver is infinite. Based on the stability of the particles, it is better to oxidize the first silver. Copper oxide has oxidation Cuprous oxide and copper oxide, etc., have unlimited oxidation state of copper, and are easy to reduce to metal copper. Cuprous oxide is particularly preferred. These metal oxides can be commercially available or synthesized by known synthetic methods. Commercial products With C I formed into (copper) copper oxide particles with an average particle size of about 30 nanometers (nominal). Also, a synthesis method of cuprous oxide with a particle size of less than 200 nanometers. The compound is synthesized in a polyalcohol solvent at about 20 ° C (Angewandt Chemie Internation Edtiion, No. 40, vo 1.2 'P · 359.2001), an organic copper compound (copper-N-nitrosophenylhydroxylamine Compound) in the presence of a protective agent such as cetylamine, in a passive ambient gas, at a high temperature of about 300 ° C (J.Am.Chem.Soc., 1999, vol. 121, p. 1 1 5 95). Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. The particle size of the metal oxide used in the present invention is less than 200 nanometers. It only needs to be fused between particles during heat treatment. One of the metal oxide particles Parts can also be replaced with materials other than reducible metal oxides. Materials other than reducible metal oxides are, for example, metals, metal oxides that are not reduced by heating below 500 ° C, or organic compounds, the central part Core metal-shell type with surface covered with metal oxide The metal-metal oxide composite fine particles are an example. The metal oxide fine particles used in the present invention may be weakly agglomerated with each other in the metal oxide dispersion, and can be dispersed again before printing so as to prevent the aggregates from clogging when coated by screen printing. Nets are better. Also, for inkjet coating purposes, the paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) -12- 1236931 Printed by A7 _ __B7____ Explanation of the invention (9) • In the case, the particle size of the aggregate is preferably less than 100 nanometers. These aggregates can be secondary aggregates, and their particle size can be measured by laser scattering. The weight of the metal oxide is preferably 5 weight% to 95 weight%, and more preferably 10 weight% to 80 weight%. When it is less than 5% by weight, the thickness of the metal film obtained by a single coating and firing is low, and when it exceeds 95% by weight, the dispersion viscosity is too high, and there is a problem that it is difficult to apply it to a substrate. Examples of the dispersion medium based organic solvent and / or water 'organic dispersion medium used in the present invention include liquid alcohol-based solvents, ketone-based solvents, amidine-based solvents, ester-based solvents, and ether-based solvents. Here, the alcohol-based solvents include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, secondary butanol, tertiary butanol, n-pentanol, isoamyl alcohol, and 2-methylbutanol. Alcohol, secondary pentanol, tertiary pentanol, 3-methoxybutanol, n-hexanol, 2-methylpentanol, secondary hexanol, 2-ethylbutanol, secondary heptanol, heptanol 3, n-octanol, 2-ethylhexanol, secondary octanol, n-nonanol, 2,6-dimethylheptanol-4, n-decanol, secondary undecanol, trimethylnonanol, Monotetradecanol, secondary heptadecanol, phenol, cyclohexanol, methylcyclohexanol, 3,3,5-trimethylcyclohexanol, benzyl alcohol, diacetone alcohol and other monoalcohol solvents, and ethyl alcohol Glycol, 1 '2-propanediol' 1,3-butanediol, pentanediol-2,4, 2-methylpentanediol-2,4, hexanediol-2,5, heptane-2 , 4,2-ethylhexylene glycol-1,3, diethylene glycol, dipropylene glycol, hexanediol, octanediol, triethylene glycol, tripropylene glycol, glycerol and other polyol solvents, and ethylene glycol Monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol monophenyl ether, ethylene glycol monohexyl Butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether Paper size applicable to Chinese National Standard (CNS) A4 (210 X297 mm) (Please read the precautions on the back before filling this page)- 13- 1236931 A7 ___ B7_ V. Description of the invention (10) Ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether (Please read the precautions on the back before filling this page ), Propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether and other polyol partial ether solvents. These alcohol solvents can be used singly or in combination of two or more kinds. Ketone solvents include acetone, methyl ethyl ketone, methyl n-propyl ketone, methyl n-butyl ketone, diethyl ketone, methyl isobutyl ketone, methyl n-pentyl ketone, ethyl n-butyl ketone, and methyl ethyl ketone. N-hexyl ketone, diisobutyl ketone, trimethylnonanone, cyclohexanone, 2-cyclohexanone, methylcyclohexanone, 2,4-pentanedione, acetone acetone, methylphenyl ketone , And acetoacetone, 2,4-hexanediol, 2,4-heptanedione, 3,5-heptanedione, 2,4-octanedione, 3,5-octanedione, 2,4- Nonanediol, 3 ', 5-nonanedione, 5-methyl-2,4-hexanedione, 2,2,6,6-tetramethyl-3,5-heptanedione, 1,1, 1,5,5,5-hexafluoro-2,4-heptanedione, etc./3-diones, etc. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, methylamine solvents are methylformamide, N-methylformamide, N, N-dimethylformamide, N-ethylformamide, N, N- Diethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, N-ethylacetamide, N, N-diethylacetamide, N -Methylpropionamine, N-methylpyrrolidone, N-methylpyrrolidone, N-methylpyridine, N-methylpyrrolidine, N-ethylpyrrolidone, N-ethylpyrrolyl Piperidine, N-ethylpyrrolidine and the like. I ester solvents include diethyl carbonate, vinyl carbonate, propylene carbonate, diethyl carbonate, methyl acetate, ethyl acetate, T-butyrolactone, r-valerolactone, n-propyl acetate, and isopropyl acetate Propyl ester, n-butyl acetate, isobutyl acetate, secondary butyl acetate, n-amyl acetate, secondary amyl acetate, 3-methoxy acetate This paper is sized for the Chinese National Standard (CNS) A4 (210X297) -14) 1236931 A7 B7 V. Description of the invention (11) (Please read the precautions on the back before filling out this page) '' Butyl Butyl Acetate, 2-Ethyl Butyl Acetate, 2-Ethyl Acetate 2- Ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, methyl cyclohexyl acetate, n-nonyl acetate, methyl ethyl acetate, ethyl ethyl acetate, ethylene glycol monomethyl ether acetate, acetic acid Ethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl acetate, Propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, acetic acid Dipropylene glycol monoethyl ether, ethylene glycol diacetate, methoxytriethylene glycol ester, ethyl propionate, n-butyl propionate, isoamyl propionate, diethyl monoacetate, oxalic acid N-butyl ester, methyl lactate, ethyl lactate, n-butyl lactate, n-pentyl lactate, diethyl malonate, dimethyl phthalate, diethyl phthalate, and the like. These ester solvents can be used singly or in combination of two or more kinds. The ether solvents are dipropyl ether, diisopropyl ether, dioxane, tetrahydrofuran, tetrahydropyran, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether, propylene glycol dimethyl ether, and propylene glycol. Diethyl ether 'propylene glycol dipropyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, and the like. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs These decentralized media can be used alone or in combination of two or more decentralized media. Especially for inkjet coating applications, metal oxides with a particle size of less than 200 nm can be uniformly dispersed and the viscosity of the metal oxide dispersion can be reduced. The metal oxide dispersion of the present invention must contain a polyol and / or a polyether compound in a dispersion medium. Polyols and polyether compounds can be solid or liquid. When the polyol or polyester compound contained in the metal oxide dispersion is a solid, it can be used by dissolving in the above organic solvent and / or water dispersion medium. The paper size of the other party applies the Chinese National Standard (CNS) A4 specification (210X297 mm) — -15-1236931 A7 B7. V. Description of the invention (12) Polyols and polyether compounds contained in the metal oxide dispersion When it is a liquid, it itself has the function of dispersing media. (Please read the precautions on the reverse side before filling out this page) In the present invention, polyol refers to compounds with 2 or more hydroxyl groups. The polyether compound also refers to a compound having two or more ethers. Here, compounds with a combination of hydroxyl groups and ethers of 2 or more are classified as one according to the following criteria; Compounds are classified as polyols, (丨 丨) and nl < n2 or ni = n2, the olefin is a polyether compound. For example, maltotriose is a trisaccharide with 11 hydroxyl groups and 5 ethers in the molecular skeleton, which are classified as polyhydric alcohols according to the above standards. In addition, triethylene glycol is classified as a polyether compound according to the above-mentioned criteria because of the combination of the hydroxyl group and the ether 2 in the molecular skeleton. Printed by the Employees' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. The dispersion of metal oxide particles can be improved when the metal oxide dispersion contains a polyol. Polyols are, for example, ethylene glycol, diethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2 -Butene-1,4-diol, 2,3-butanediol, pentanediol, hexanediol, octanediol, 1,1,1-trimethylolethane, 2-ethyl-2 -Hydroxymethyl-1,3-propanediol, 1,2 '6-hexanetriol, 1,2,3-hexanetriol, 1,2,4-butanetriol, and the like. It is also possible to use sugar alcohols such as glycerin, threitol, erythritol, pentaerythritol, .pentaerythritol, and hexitol. Pentaerythritol contains xylitol, ribitol, and arabitol. The "hexitol" includes mannitol, sorbitol, and sweet alcohol. Glyceraldehyde, dihydroxyacetone, threose, erythulose, erythrose, arabinose, ribose, ribulose, xylose, xylulose, lyxose, glucose, fructose, and mannose can also be used. , Idose, sorbose, gulose, talose, tagatose, galactose, allose, atroose, lactose, isomalt, and heptane. Paper standards apply to Chinese National Standard (CNS) A4 specifications (210 X297 mm) -16-1236931 A7 —B7 V. Description of the invention (I3) Sugars such as sugar, heptose, maltobiose, lettuce disaccharide, and trehalose. These polyhydric alcohols are advantageous in reducing metal oxides because of their reducing properties. (Please read the precautions on the back before filling in this page.) Especially good polyols are polyols with 10 or less carbon atoms. Among them, those with liquid viscosity and low viscosity are more suitable for dispersing media as mentioned above. Such polyols are, for example, ethylene glycol, diethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol , 2,3-butanediol, pentanediol, hexanediol, octanediol and the like. '' Polyols are especially sugar alcohols such as glycerol, threitol, erythritol, pentaerythritol, pentaerythritol, and hexitol, because it is particularly beneficial to improve the anti-aggregation of metal oxide particles in metal oxide dispersion Sexuality is better. The preferred amount of the polyol is 0.1% by weight to 95% by weight, and more preferably 1% by weight to 90% by weight of the total weight of the metal oxide dispersion. If it is less than 0.1% by weight, the effect of improving the dispersibility of the metal oxide particles is small. If it exceeds 95% by weight, the amount of the metal oxide in the dispersion is small, and it is difficult to form a high-quality metal film, which is not good. These polyols can be used singly or as a mixture of most polyols. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, the metal oxide dispersion contains polyether compounds, and the denseness of the metal film obtained by calcining the dispersion can improve the adhesion and the adhesion to the substrate. The polyether compound is a compound having an ether bond in the skeleton, and is preferably uniformly dispersed in a dispersion medium. The microstructure of the metal thin film obtained by using the metal oxide dispersion varies depending on whether the metal oxide dispersion contains a polyether compound or not. When the content of the polyether compound in the metal oxide dispersion accounts for less than 0.1% by weight of the total weight of the metal oxide dispersion, the obtained metal film is a porous metal film having a porous structure with a pore diameter of 1 micrometer or less. On the other hand, the paper size of the metal is applicable to the Chinese National Standard (CNS) A4 specification (210X 297 mm)-"-17- 1236931 A7 _B7__ V. Description of the invention (M) The polyether compound content in the oxide dispersion accounts for the metal When the total weight of the oxide dispersion is 0.1 to 70% by weight or less, the resulting metal thin film has very few pores and its pore diameter is small, and therefore, the compactness is further improved. The reason for adding the polyether compound to the metal oxide dispersion to improve the compactness and adhesion of the metal film obtained by calcination is not sure, but it should be to prevent local granulation between the metal oxide particles during calcination. And a very small amount of the polyether compound is left in the metal film as a binder or at the interface with the substrate directly or through carbon reduction. Polyether compounds are decomposed by metals that are susceptible to reduction by metal oxides, especially those which are susceptible to low-temperature catalytic decomposition in the presence of hydrogen and other gases in the presence of gases, and are more likely to disappear. Polyether compounds are advantageous in reducing metal oxides because of their reducing properties. From the viewpoint of the dispersibility of the metal oxide fine particles into the dispersion medium, the polyether compound is preferably an amorphous polyether compound, especially a linear or cyclic oxyalkylene group having a repeating unit of carbon and 2 to 8 atoms. An aliphatic polyether is preferred. The molecular structure of the repeating unit is a linear or cyclic alkenyl aliphatic polyether having 2 to 8 carbon atoms. The molecular structure may be cyclic, linear, or branched, or a polyether copolymer of 2 or more members or Polyether block copolymer of more than 2 yuan. Specifically, there are polyether monopolymers such as polyethylene glycol, polypropylene glycol, and polybutylene glycol, ethylene glycol / propylene glycol, and a binary copolymer of ethylene glycol / butylene glycol, and ethylene glycol / propylene glycol / Linear tertiary copolymers such as ethylene glycol, propylene glycol / ethylene glycol / propylene glycol, ethylene glycol / butanediol / ethylene glycol, but are not limited thereto. Block copolymers include binary block copolymers such as polyethylene glycol polypropylene glycol, polyethylene glycol polybutylene glycol, and the like, as well as polyethylene glycol polypropylene glycol polyethylene glycol, polypropylene glycol polyethylene glycol polypropylene glycol, This paper size applies the Chinese National Standard (CNS) Α4 specification (210 × 297 mm) (Please read the precautions on the back before filling this page) Binding-Order printed by the Intellectual Property Bureau of the Ministry of Economic Affairs Consumer Cooperatives -18-1236931 A7 ____B7_ 5 Description of the invention (15) Polyether block copolymers such as polyethylene glycol, polybutylene glycol, polyethylene glycol, and other linear three-block block copolymers. (Please read the notes on the back before filling this page} The polyether compound used in the present invention may also contain other molecules in the molecular structure. Energy groups such as alcohol groups, ester groups, epoxypropyl groups, imino groups, Alkyl, amidino, amine, phenyl, aldehyde, carbonate, isocyanate, sulfonamido, etc., or a combination of these groups, containing alkyl ester, alkylamido, and alkyl carbonate Substituents such as ester groups, but are not limited thereto. It also includes polymerizable vinyl, vinylidene, vinylidene, glycidyl, allyl, and acrylate and methacrylate groups containing these groups. These functional groups may have many in the molecule, such as sugar, or polyalcohols such as sugar alcohol in the molecule. The employee's cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs prints the polymer containing hydroxyl groups in the sugar alcohol. The structure of the chain is based on the hydroxyl-binding polymer chains contained in glycerol, threitol, erythritol, pentaerythritol, pentaerythritol, hexitol, and the like. Examples include glycerol polyethylene glycol polypropylene glycol, erythritol • Polyethylene glycol, polypropylene glycol, polyethylene glycol, etc. Specific examples of sugar chains include glyceraldehyde , Dihydroxyacetone, threose, erythritol, erythritol, arabinose, ribose, ribulose, xylose, xylulose, lyxose, glucose, fructose, mannose, idose, sorbose , Gulose, talose, tagatose, galactose, allose, altroose, lactose, isomaltose, glucoheptose, heptose, maltotriose, lettuce triose, trehalose, etc. The aliphatic polyether used in the present invention has no particular limitation on its terminal group. The terminal group has a linear, branched or cyclic alkyl ether group, an alkyl ester group, and an alkyl group having a hydroxyl group and a carbon number of 1 to 8. Modifiers such as aminoamine, alkylcarbonate, urethane, or trialkylsilyl. The specific examples of the modification of the terminal group of aliphatic polyether are listed below. This paper's dimensions apply to Chinese national standards (CNS) A4 specification (210X297 mm) -19- 1236931 A7 ____ B7 V. Description of the invention (16) (Please read the notes on the back before filling this page) At least one terminal alkyl etherification example is methyl ether , Ether, propyl ether, glycidyl ether, etc. Specific examples include polyethylene glycol monomethyl ether, polyethylene glycol dimethyl ether, polypropylene Glyme, polyisobutylene glycol dimethyl ether, polyethylene glycol diethyl ether, polyethylene glycol monoethyl ether, polyethylene glycol dibutyl ether, polyethylene glycol monobutyl ether, polyethylene glycol bicyclo Oxypropyl ether, polyethylene polypropylene glycol dimethyl ether, glycerin polyethylene glycol-dimethyl ether, pentaerythritol polyethylene glycol tetramethyl ether, pentaerythritol polyethylene glycol pentamethyl ether, sorbitol polyethylene glycol hexamethyl ether Etc. It is not known that there are ester-based aliphatic polysaccharides, and at least one end is, for example, acetate, propionate, acrylate, methacrylate, or benzoate. It is also suitable for esterification of the terminal carboxyalkyl group. Preferred examples include polyethylene glycol monoacetate, polyethylene glycol diacetate, polypropylene glycol monoacetate, polypropylene glycol diacetate, and polyethylene. Diethylene glycol dibenzoate, polyethylene glycol diacrylate, polyethylene glycol monomethacrylate, polyethylene glycol dimethacrylate, polyethylene glycol biscarboxymethyl ether dimethyl ester, polypropylene glycol Dicarboxymethyl dimethyl ether, glycerol polyethylene glycol triacetate, pentaerythritol polyethylene glycol tetraacetate, pentaerythritol Polyethylene glycol pentaacetate, sorbitol polyethylene glycol hexaacetate, etc. The Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs has printed aliphatic polyethers with amido groups at the end, which are methylated with at least one terminal carboxyl group, and then amidolated, or modified with hydroxyl groups The applicable ones include polyethylene glycol bis (carboxymethyl ether dimethylamine), polypropylene glycol, alcohol bis (carboxymethyl ether dimethylamine), and polyethylene glycol bis (carboxymethyl ether diethylamine). Fluorenamine), glycerol polyethylene glycol tricarboxymethyl ether dimethylamine, pentaerythritol polyethylene glycol tetracarboxymethyl ether dimethylamine, pentaerythritol polyethylene glycol pentacarboxymethyl ether dimethylamine 、 Sorbitol polyethylene glycol hexacarboxymethyl ether dimethylamidamine This paper size is applicable to China National Standard (CNS) A4 specification (210X29 < 7 mm) 1236931 A7 ______ B7 5. Description of the invention (17) and so on. (Please read the precautions on the back before filling in this page) Aliphatic polyethers with alkyl carbonate groups at the ends, such as those with at least one end of the above ene glycols added with a methyl ester group, specifically bismethyl Oxycarbonyloxy polyethylene glycol, diethoxycarbonyloxy polyethylene glycol, diethoxy mineral oxypolypropylene glycol, bis tertiary butoxycarbonyloxy polyethylene glycol, and the like. Aliphatic polyethers modified with urethane or trialkylsilyl groups at the ends can also be used. The modification of trialkylsilyl group is preferably modified by trimethylsilyl group, which can be modified by trimethylchlorosilane, trimethylchlorosilylacetamide or hexamethyldisilazane. . From the viewpoint of the solubility in the dispersion medium and the dispersibility of the metal oxide, the best terminal group of the aliphatic polyether is a low-molecular-weight liquid substance in the hydroxy polyether compound, which itself can be used as a dispersion medium. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs for the calcination of metal oxide dispersions containing polyether compounds for high electrical conductivity. Metal thin films, polyether compounds are preferably those that can be incinerated at low temperature, and the molecular weight is 150 to 6000 is preferred, and 250 to 1,500 is more preferred. If the polyether compound used has an excessively large molecular weight, it will not be easily incinerated during calcination, and the amount of the polyether compound remaining in the metal film will be large. When the amount of the polyether compound remaining in the metal film is large, there is a problem that the volume resistance of the metal film is high. On the other hand, when the molecular weight of the polyether compound is too large, the dispersibility in the dispersion medium is insufficient and unfavorable. On the other hand, if the molecular weight is too small, the heat-treated metal thin film has low film-forming property and denseness, which is not good. The amount of the polyether compound in the metal oxide dispersion is 0.1 to 70% by weight, and more preferably 1 to 50% by weight. When the amount of polyether compound is less than 0.1% by weight, it is reduced from metal oxygen. The paper size is applicable to China National Standard (CNS) A4 (210X 2 叼 mm) -21- 1236931 A7 __B7 V. Description of the invention (18) The metal of the compound has low interparticle density and tends to decrease the adhesion to the substrate. On the other hand, when the polyether compound is added in an amount of more than 70% by weight, (please read the precautions on the back before filling out this page) • The viscosity of the metal oxide dispersion tends to increase and is not good. The method of dispersing the metal oxide in the dispersion medium may be a method of generally dispersing powder in a liquid. For example, the ultrasonic method, the mixer method, the three-light method, the two-roll method, the vertical ball mill, the Banbury mixer, the paint shaker, the kneader, the homogenizer, the ball mill, the sand mill, and the like. Dispersion is usually performed by combining a plurality of such dispersing means. When the polyol (and / or polyether compound) is in a liquid state, the polyol (and / or polyether compound) and the metal oxide can be added to the dispersion medium and dispersed at the same time. On the other hand, when the polyol and / or polyether compound is in a solid state, it is preferable to dissolve the polyol (and / or polyether compound) in a dispersion medium, and then add a metal oxide to the resulting solution for dispersion treatment. These dispersion treatments can be performed at room temperature, and in order to reduce the viscosity of the solvent, they can also be heated under heat. In the dispersion medium used in the present invention, a metal oxide having a particle size of less than 2000 nanometers is synthesized, and the dispersion treatment of the metal oxide can be omitted. As a dispersion medium for a metal oxide dispersion, a polyhydric alcohol having a carbon number of 10 or less is particularly preferred, and the above-mentioned polyether compound is contained in the dispersion medium. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs to make the metal oxide dispersion contain metal powder other than metal oxide particles, which can improve the characteristics of the metal bonding layer obtained by heat treatment, and it is better to reduce the amount of metal oxide particles. . There are no special restrictions on the metal powders that can be used, such as gold, silver, copper, palladium, platinum, nickel, chromium, aluminum, tin, zinc, titanium, tungsten, giant, barium, rhodium, ruthenium, star, bismuth, iridium, cobalt , Indium, iron, lead, etc., one or more metal powders can be selected according to the purpose. For high conductivity, silver, nickel, and copper, which are commercially available at low cost, are particularly preferred. Silver can be applied to Chinese paper (CNS) A4 size (210 X 297 mm) because it can be given to metal. Paper size is -22-1236931 A7 _B7____ 5. Description of the invention (θ film has high oxidation resistance, so it has better anti-migration. If necessary, you can add copper powder with strong anti-migration to the metal bonding layer. (Please read the precautions on the back and fill in this page) There are no special restrictions on the particle size of these metal powders, which should be better used according to the purpose. Particle size of metal powder. When the metal film is calcined, the particle size of the metal powder is preferably 100 micrometers or less, more preferably 10 micrometers or less. When the metal powder particle size is 100 micrometers or more, the size of the metal powder and the metal oxide particles are too large. The smoothness of the metal bonding layer is not good. When the metal oxide dispersion is used in inkjet inks, the particle size of the metal powder is preferably 200 nm or less, and more preferably 100 nm or less. The amount of the metal powder of the oxide dispersion is based on the total content of the metal powder and the metal oxide fine particles, and preferably accounts for 5 wt% to 95% by weight of the total weight of the metal oxide dispersion. Metal powder and metal oxide fine particlesThe weight ratio is preferably 9: 1 to 1: 9. When the content of metal powder and metal oxide particles is less than 5% by weight, the addition effect is small, and if it exceeds 95% by weight, the viscosity of the oxide dispersion increases and disperses. The coating and filling of the body is difficult and unsatisfactory. When the weight ratio of the metal powder to the metal oxide particles exceeds the range of 9: 1 to 1: 9, the mixing effect of the two particles becomes small and unsatisfactory. Bureau of Intellectual Property, Ministry of Economic Affairs It is better for employees' consumer cooperatives to add a thermosetting resin to the above metal oxide dispersion. It is better to increase the adhesion to the metal surface and increase the strength by heat curing. The available thermosetting resin must be soluble in the dispersion medium used without damage. There are no special restrictions on the dispersibility of metal oxide dispersions. There are, for example, epoxy resins, epoxy resins, epoxy resins, polyimide resins, polyurethanes, melamine resins, urea resins, etc. Epoxy resins such as bisphenol Type A epoxy resin, bisphenol F type epoxy resin. The paper size is applicable to Chinese National Standard (CNS) A4 specification (210X 297 mm) " — ~~ 一--23- 1236931 A7 B7 V. Description of the invention ( 20) (Please read the precautions on the back before filling this page) grease, (cresol) lacquer type epoxy resin, halogenated bisphenol type resin, resorcinol type, tetrahydroxyphenol ethane type, polyalcohol Glycol type, triglyceride type, polyolefin type, epoxidized soybean oil, cyclopentadiene dioxide, ethylene cyclohexene dioxide, etc. Liquid epoxy resins are preferred due to their low viscosity, examples of which are benzene Oxyalkyl monoglycidyl ether, bisphenol A diglycidyl ether, propylene glycol diglycidyl ether, propylene glycol diglycidyl ether, hexanediol diglycidyl ether, hydrogenated bisphenol A diepoxy Propylene ether, neopentyl glycol diglycidyl ether, glycerol diglycidyl ether, N, N-glycidylaniline, N, N-glycidyltoluidine, trimethylolpropane Among liquid epoxy resins, such as glycidyl ether, glycerol triglycidyl ether, and various liquid polysiloxane diglycidyl ethers, alcohol type epoxy resins that can be well dispersed in a polyol dispersion medium are preferred. There are, for example, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, and the like. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs The epoxy resin hardener used in the present invention can be a general epoxy hardener. For example, aliphatic polyamine-based triethylenetetramine, m-xylylenediamine, etc., aromatic amine-based phenylenediamine, diaminodiphenyl, etc., and tertiary amines include benzyldimethylamine, Dimethylaminomethylphenol and the like, acid anhydrides include phthalic anhydride and hexahydrophthalic anhydride, and trifluoroboramine complexes include BF3-piperidine complex and the like. A bisphenol compound such as bisphenol A may be used. Diamine, 2-ethyl-4-methylimidazole, ginsyl (methylamino) silane and the like can also be used. Resin-based hardeners include polyamidoamine resins made of linolenic acid dimer and ethylenediamine, polythioether resins with cyano groups at both ends, and lacquer-based phenol resins. These can be used alone or in combination of two or more. The amount of hardener added varies with the type of hardener. For example, the standard of this paper, such as acid anhydride, is applicable to Chinese National Standard (CNS) A4 (210X297 mm) -24- 1236931 A7 __ _ B7 V. Description of the Invention (21) ( Please read the precautions on the back before filling this page.) When reacting with the epoxy group based on stoichiometry, the optimum addition amount is determined by the epoxy equivalent. When the catalyst is reacted, it is generally 3 to 30 weight ° /. . At this time, when the room temperature reactivity of the hardener is high, the liquid containing the initiator may be mixed into the adhesive immediately before use, or the hardener may be encapsulated in vesicles such as gelatin of about 100 microns to make microcapsules. Other examples of thermosetting resins are polyimide resins, which are precursors of polyfluorene. The amino acid solution is obtained by heating and condensing. The polyamic acid can be used in the present invention. Examples of tetracarboxylic dianhydrides include pyromellitic dianhydride, 3,3 >, 4,4, -diphenylketone tetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,2,5,6, -naphthalenetetracarboxylic dianhydride, 3,3 /, 4,4 / -biphenyltetracarboxylic dianhydride, 2 , 2 /, 3,3 / -biphenyltetracarboxylic dianhydride, 2,3,3- —, 4biphenyltetracarboxylic dianhydride, 2,3,3 >, 4 〃 -diphenylketone tetracarboxylate Acid dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis [5- (3, cardiodicarboxyphenoxy) phenyl] propane dianhydride, etc. Amine compounds include, for example, m-phenylenediamine, p-phenylenediamine, 2,4-toluenediamine, 3,3 diamino diphenyl ether, 3,4 'diamino diphenyl ether, 4,4' diamine Diphenyl ether, 3,3 'diamine monobenshuo, 4,4-monoamino monobenzenshuo, 3,4-diaminodiphenylshuwan, 3, printed by Consumer Cooperative of Intellectual Property Bureau, Ministry of Economic Affairs 3-diaminodiphenylmethane, 4,4 > -diaminodiphenylmethane, 3,4, -diaminodiphenylmethane, 4,4 > -diaminodiphenylmethylene, 3 , 3-diaminodiphenyl ketone, 4〆 / -diaminodiphenyl ketone, 3,4, -diaminodiphenyl ketone, 2, 2 / -Bis (4-aminophenyl) propane and the like. In the present invention, the amount of the thermosetting resin added to the metal oxide dispersion is preferably 0.1 to 20% by weight, and more preferably 1 to 10% by weight based on the total weight of the dispersion medium, the polyether compound, and the thermosetting resin. The amount of thermosetting resin is not the same as the size of the paper. The Chinese national standard (CNS) A4 specification (210X297 mm> -25- 1236931 A7 __ B7_ V. Description of the invention (22) and 0.1% by weight are small, but if it exceeds 20 The weight% is not suitable as a material for forming a metal thin film because the conductivity of the metal bonding layer is significantly reduced. (Please read the precautions on the back before filling this page.) In the present invention, the polyol and polyether compound are reducing and have reducing metals. The effect of oxides, in addition to polyhydric alcohols and polyether compounds, it is better to add a reducing agent that can reduce the metal oxide to the metal oxide dispersion, which can reduce the metal oxide more easily. At this time, only It must be able to reduce metal > oxides. There are no special restrictions on the reducing agents that can be used. Both inorganic reducing agents and organic reducing agents are possible. Inorganic reducing agents include hydrogen compounds such as sodium borohydride and lithium borohydride, sulfur compounds such as sulfur dioxide, and sulfurous acid. Salts of lower oxides such as salts, hydrogen iodide, carbon, etc. Organic reducing agents other than polyols and polyether compounds include, for example, aldehydes, hydrazines, diimines, and oxalic acid. Aldehydes include, for example, formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, isobutyraldehyde, valeraldehyde, isovaleraldehyde, trimethylacetaldehyde, hexanal, heptaldehyde, caprylic acid, nonanoic acid,-wake up, laurel Acid, thirteen, myristic aldehyde, printed by the consumer co-operatives of the Intellectual Property Bureau of the Ministry of Economy, pentaaldehyde, palmityl, heptaaldehyde, stearyl, and other aliphatic saturated aldehydes, glyoxal, succinaldehyde Aliphatic, unsaturated aldehydes, acrolein, crotonaldehyde, propynal, etc.Saturated aldehydes, benzaldehyde, o-tolualdehyde, m-tolualdehyde, p-tolualdehyde, salicylaldehyde, cinnamaldehyde, α-naphthaldehyde, / 3-naphthalene Aromatic aldehydes such as aldehydes, heterocyclic aldehydes such as furfural, etc. Diimines are, for example, azodicarboxylates, hydroxylamine-0-sulfonic acid, N-propadienesulfonylhydrazine, or N-fluorenylsulfonylhydrazine It is obtained by thermal decomposition. N-propadienesulfonylhydrazine or N-fluorenylsulfonium is, for example, p-toluenesulfonylhydrazine, benzenesulfonylhydrazine, 2,4,6-isopropylbenzenesulfonylhydrazine, Chloroethylhydrazine, o-nitrobenzenesulfonylhydrazine, m-nitrobenzenesulfonylhydrazine, p-nitrobenzenesulfonylhydrazine, etc. This paper size applies to China National Standard (CNS) A4 specification (210 × 297 mm> -26- 1236931 Warp Printed by the Ministry of Intellectual Property Bureau Consumer Cooperative A7 B7 ____ V. Description of the Invention (2) The content of reducing agents other than polyols and polyether compounds accounts for the total weight of the metal oxide dispersion 0.1 to 70 weight ° / It is preferably 0.1 to 50% by weight, more preferably 0.1 to 20% by weight, and even more preferably 1 to 10% by weight. In the present invention, in order to improve the strength and the substrate of the metal film obtained by calcination, For the adhesiveness, metal oxides can also be added to the metal oxide dispersion. Metal oxide precursors. Metal oxides such as the general formula M (〇V) n, where M is a metal element. R1 is the foundation, The oxidation number of the η-based metal element. M is such as Shi Xi, Chin, Pin, Ming, etc., and the bases are, for example, methyl, ethyl, isopropyl, n-butyl, tertiary butyl, etc. Representative metal oxides are Tetramethoxysilane, tetraethoxysilane, tetra (n-propoxy) silane, tetra (isopropoxy) silane, tetra (n-butoxy) silane, tetra (secondary butoxy) silane, tetra (Tertiary butoxy) silicon compounds such as silane, tetraethoxy titanium, tetra (n-propoxy) titanium, tetra (iso Titanium compounds such as propoxy) titanium, tetra (n-butoxy) titanium, tetra (secondary butoxy) titanium, tetra (tertiary butoxy) titanium, etc. These compounds are liquid and easily dispersed in metal oxidation A dispersion is therefore preferred. It is also possible to use a metal alkoxide represented by 1 or more), and the metal is directly added with an organic group R2. Examples of the organic group R2 include fluorenyl, ethyl, propyl, phenyl, and butyl. The method of dispersing metal powder, thermosetting resin, reducing agent, metal alkoxide and other materials in the metal oxide dispersion can be ultrasonic method, mixer method, two-roll method, one-roll method, vertical ball mill, bauber Mixer, paint shaker, kneader, homogenizer, ball mill, sander and other general methods. These dispersions can also be performed simultaneously with the dispersion of metal oxides and polyols (and / or polyether compounds) in a dispersion medium. This paper applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) — -27- (Please read the notes on the back before filling out this page) Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs, M Industrial Consumer Cooperative, 1236931 'A7 _____ B7 V. Description of the invention (Secondly, a method for forming a metal thin film on a substrate using the metal oxide dispersion of the present invention (a method for forming a substrate and a laminate formed by a metal thin film). The substrate may be an inorganic or organic substrate. An inorganic substrate may be used Glass substrates, semiconductor substrates such as Shi Xi, germanium, compound semiconductor substrates such as gallium-arsenic, indium-antimony, etc. 'Those surfaces can also be formed with thin films of other substances before use. At this time, the tritium film can be a Ming, Qin, Chromium, Nickel, Copper, Silver, Group, Tungsten, Hungry, Pin, Gold and other metals' Silicon dioxide, Fluorinated glass, Phosphor glass, Borophosphoric glass, Borosilicate glass, Polycrystalline sand, Alumina, Titanium oxide , Oxidized oxide, nitrided sand, titanium nitride, nitrided giant, boron nitride, hydrogenated silsesquioxane, ITO (indium tin oxide) and other inorganic compounds, methylsilsesquioxane, amorphous carbon, fluorinated Amorphous carbon, Films made of fluorene imine, etc. Organic substrates are not limited if they are not damaged by heat at the heat treatment temperature of the metal oxide dispersion. For example, polyimide substrates, polyethylene terephthalate (PET) can be used. Substrates, aromatic polyamide substrates, epoxy substrates, fluororesin substrates, etc. Before forming a metal thin film, in order to improve adhesion, it can be treated by physical methods such as plasma treatment and electron beam treatment, or dense. Adhesive accelerators can be treated by chemical methods. Adhesion accelerators can be so-called silane coupling agents, chelates, etc. Preferred are 3-aminopropyltrimethoxysilane and 3-aminopropyltriethoxy. Silane, N (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, Vinyltrichlorosilane, vinyltriethoxysilane, 3-chloropropyltrimethoxysilane, chloropropylmethyldichlorosilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyl This paper size applies to China National Standard (CNS) A4 (210X297 mm) (Please read the precautions on the back before filling Page)
-28- 1236931 Α7 Β7 經濟部智慧財產局g(工消費合作社印製 五、發明説明（ 基甲基二乙氧基矽烷、3 -毓丙基三甲氧基矽烷、；^環氧丙氧 基丙基二甲戰基砂院、3 -ί哀氧丙氧基丙基甲基二甲氧基石夕 院、3 -甲基丙燒醯氧基丙基三甲氧基砂院、3 -甲基丙烯醯氧 基丙基甲基二甲氧基砂院、六甲基二砂院氨、乙醯基醋酸 乙酯二異丙氧基鋁、參（乙醯基醋酸乙酯）鋁、雙（乙醯基醋 酸乙酯）單乙醯基醋酸鋁、參（乙醯基醋酸）鋁等。此等密合 促進劑的塗布時，若必要可加入其它添加物，以溶劑稀釋 使用。密合促進劑之處理可用已知方法爲之。 爲提升與有機基板之密合性，亦可採用將有機基板浸 ' 泡於鹼水溶液中加熱之手法。例如，聚醯亞胺樹脂可於5 Μ 左右之氫氧化鉀溶液處理約5分鐘，醯亞胺環裂開產生羧 基以賦予釘錨效果。 使用本發明之金屬氧化物分散體，於基板上形成金屬 薄膜時，先將金屬氧化物分散體塗布於基板上。塗布方法 可用將分散體塗布於基板時所用之一般方法，有例如網印 法、浸塗法、噴塗法、旋塗法、噴墨法等。塗布分散體於 基板上之際，塗布厚度以0.1至100微米爲佳，1至30微 米更佳。 塗布分散體於基板上後，該基板於足使金屬氧化物還 原爲金屬之溫度作加熱處理，於基板上形成金屬薄膜。所 得金屬薄膜容易氧化時，以於非氧化性環境氣體中作加熱 處理爲佳。金屬氧化物難以僅藉金屬氧化物分散體中之還 原劑（多元醇、聚醚化合物、追加之多元醇及聚醚化合物以 外之還原劑）還原時，以於還原性環境氣體中煅燒爲佳。於 (請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） -29 - 1236931 • A7 _______ B7 五、發明説明（ (請先閲讀背面之注意事項再填寫本頁) 鈍性環境氣體中煅燒後，隨之於還原性環境氣體中锻燒而 得之金屬薄膜’因緻密性更加提升而更佳。非氧化性環境 氣體乃不含氧等氧化性氣體之環境氣體，有鈍性環境氣體 及還原性環境氣體。鈍性環境氣體乃指充以例如氬、氦、 氖、氮等鈍性氣體之環境氣體。還原性環境氣體指有氫、 一氧化&^等达原性氣體存在之環境氣體。此等氣體可充塡 於煅燒爐中成密閉系統煅燒，亦可使煅燒爐成爲流通系統 • ’流通此等氣體。於非氧化性環境氣體中煅燒時，可將煅 燒爐內暫時抽真空去除氧，以非氧化性氣體取代。煅燒可 於加壓環境氣體中進行，亦可於減壓環境氣體中進行。 此等還原處理中，加熱處理溫度以50°C以上500°C以 下爲佳，80°C以上40(TC以下更佳，100°C以上3 50°C以下又 更佳。本發明之金屬氧化物分散體的必要成分多元醇化合 物及/或聚醚化合物，可於如此之相對低溫焚化（或分解）。 可於不及50°C之溫度還原金屬氧化物等，金屬氧化物分散 體之保存安定性有惡化之傾向。須在高於500°C時，因超過 多數有機基材之耐熱性無法用於有機基材上，故均不佳。 經濟部智慧財產局員工消費合作社印製 ^加熱處理所需時間受金屬氧化物種類、加熱環境氣體、加 熱處理溫度以及欲施以加熱處理的分散體之形狀、大小影 響。金屬氧化物用銅之氧化物，而塗膜在微米程度，氫氣 不稀釋直接用作還原氣體，設定加熱處理溫度於2〇〇°c至 3 00°C時，1至2分鐘即可。 同一金屬氧化物，粒徑小者比粒徑大者易於還原，故 粒徑大時或須於還原環境氣體中煅燒，粒徑小時或僅於鈍 本纸張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） -30- 1236931 A7 B7 五、發明説明（2) 性環境氣體中煅燒即可還原。此時於鈍性環境氣體中锻燒 •，有可能形成實用上無問題之金屬薄膜。 煅燒本發明之金屬氧化物分散體所得1之金屬薄膜’因 以粒徑不及2 0 0奈米之金屬氧化物微粒爲原料，其微觀結 構係原料金屬氧化物微粒還原而得之一次粒徑不及200奈 米的金屬微粒互相熔合之結構’更詳言之’係一次粒徑不 及200奈米之金屬微粒互相熔合形成顆粒’顆粒間接觸、 熔合形成薄膜之結構’此可用電子顯微鏡觀察煅燒後之金 屬薄膜確認。 金屬氧化物微粒還原而得之金屬微粒互相熔合形成之 金屬顆粒之大小，隨加熱處理之環境氣體、溫度、處理時 •間而異。高溫、長時間之加熱處理則金屬顆粒更大。又， 於還原性環境氣體中加熱，則金屬顆粒有變大之傾向。金 屬顆粒愈大，且金屬顆粒互相緻密堆疊金屬顆粒間之孔結 構愈小、愈少，金屬薄膜之導電性愈接近金屬體之値，故 愈適用作導電薄膜。 如下述，隨金屬氧化物分散體中聚醚化合物含量，該 金屬氧化物分散體煅燒而成之金屬薄膜結構不同。 聚醚化合物含量占金屬氧化物分散體總重量〇. 1至7 0 重量％以下之金屬氧化物分散體煅燒成之金屬薄膜，金屬顆 粒互相緻密堆疊，體積電阻値接近金屬體之値，故適用於 例如，構裝領域有低體積電阻値之要求的配線材料、連接 材料。 另一方面，聚醚化合物之含量占金屬氧化物分散體總 本紙張尺度適用中國國家榡準（CNS ) A4規格（210X297公釐) ~ -- -31 - (請先閱讀背面之注意事項再填寫本頁) -裝· 訂 經濟部智慈財產局員工消費合作社印製 1236931 A7 ___B7 五、發明説明（j 重量不及0.1重量％之金屬氧化物分散體煅燒而得之金屬薄 膜因具多孔結構，表面積大，適用於電極等用途。以本發 (請先閱讀背面之注意事項再填寫本頁) 明之製造方法，可製造孔徑1微米以下之多孔性金屬薄膜 〇 本發明之金屬薄膜製造方法，係還原金屬氧化物微粒 產生金屬微粒，其間熔合而得金屬薄膜之方法，因利用還 原所生粒子間之自發性熔合引力，不必加壓。又，如上述 ’金屬氧化物微粒之一次粒徑不及200奈米，非常之小， 且聚醚化合物及多元醇本身具還原性，金屬粒子間應易有 自發性熔合。多元醇或聚醚化合物於相對低溫煅燒，因本 身氧化、分解、揮發、金屬薄膜中不易有此等絕緣成分殘 .留，故金屬薄膜之體積電阻値低。又，如上述，調整金屬 氧化物分散體中聚醚化合物之含量，即易得多孔性金屬薄 膜。再以控制基板上金屬氧化物分散體之塗布厚度，可任 意控制所得金屬薄膜之膜厚，尤以於形成微細電路所需之 極薄金屬層的容易形成之優點，特別適用於背膠金屬箔等 用途。 經濟部智慧財產局員工消費合作社印製 金屬氧化物分散體含金屬粉時，經煅燒得金屬粉間金 屬氧化物微粒還原產生之金屬微粒熔合而成之金屬薄膜。 因此，本發明所得金屬薄膜之金屬成分包括金屬氧化物還 原而得之金屬，及所添加金屬粉之金屬。金屬氧化物還原 •得之金屬與金屬粉之金屬可係相同或不同。可構成金屬薄 膜之金屬有例如金、銀、銅、鈀、鉑、鎳、鉻、鋁、錫、 鋅、鈦、鎢、钽、鋇、鍺、釕、餓、鉍、銥、鈷、銦、鐵 本紙張尺度適用中國國家標準（CNS) A4規格（210X 297公釐） — -32- 1236931 A7 B7 ’五、發明説明（ 、鉛，金屬薄膜含此等金屬之至少其一。 本發明之金屬薄膜製造方法係於相對低溫煅燒當場（ ins itu)產生金屬微粒，使粒子間熔合製造金屬薄膜之方法， ，所用原料並非昂貴之金屬微粒，而係價廉之金屬氧化物 ’故有能廉價製造金屬薄膜之優點。又，金屬氧化物微粒 不須預先分散於結晶高分子等之特殊媒體（其需高溫分解）， 故可於5 00 °C以下之相對低溫以加熱處理形成金屬薄膜，因 此，具有製程成本低之優點。易言之，本發明之金屬薄膜 .的製造方法，係使用低價原料，以低溫煅燒程序即可製造 金屬薄膜之方法。 實施例 以下藉實施例具體說明本發明，惟本發明不限於此。 本發明中銅氧化物粒子之一次粒徑，及煅燒所得金屬 薄膜之表面形態，係用日立製作所製之掃瞄式電子顯微鏡（ S-47 0 0)觀察表面而測定。金屬氧化物分散體中之金屬氧化 物的平均二次粒徑，係用堀場製作所製之雷射散射粒度布 計（LA-920)測定。所得金屬薄膜體積電阻率，係用低電阻率 '計（LOWRESTER GP(三菱化學（股）製）以四短針法求出。 (實施例1 :調製氧化銅微粒分散體及製造多孔性銅薄膜之 例） 於一乙一醇5克加入氧化銅奈米粒子（粒徑1 〇至1 〇 〇 奈米’標稱平均粒徑30奈米，CI化成（股）製）5克，用 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） (請先閱讀背面之注意事項再填寫本頁) -裝. 訂 經濟部智慈財產局貨工消費合作社印製 -33- 1236931 經濟部智慧財產局員工消費合作社印製 A7 _ B7 五、發明説明（3() KEYENS(股）製攪拌脫泡機（HM-5 00)以攪拌模式1〇分鐘， 脫泡模式5分鐘之條件作分散處理，得氧化銅微粒分散體 。將所得氧化銅微粒分散體塗布於載玻片上成爲長2公分 、寬1公分、厚20微米。將上述載玻片送入煅燒爐內，爐 內以真空泵脫氣後，以1公升/分鐘流量之氫氣流通。煅燒 爐溫度由室溫以1小時升溫至250°C，達250°C後再於該溫 度加熱1小時煅燒。冷卻後取出載玻片加以覲察，所得銅 薄膜係厚4微米、孔徑約0.3微米之多孔性薄膜。該薄膜易 於從載玻片以膠帶剝離，該薄膜之體積電阻値爲5χ 1(Γ5歐 姆公分。 (實施例2 :調製氧化銅微粒分散體，製造多孔性銅薄膜之 例） 分散媒體改用乙二醇，以如同實施例1之分散方法調 製氧化銅微粒分散體。煅燒溫度改爲200°C以外如同實施例 1作氧化銅分散體之氫煅燒。該薄膜易於從載玻片以膠帶剝 .離，該薄膜之體積電阻値爲6x 1(Τ5歐姆公分。冷卻後取出 載玻片作觀察，則形成有厚4微米、孔徑約〇·2微米之多孔 結構的多孔性銅薄膜。 (實施例3 :調製氧化銅微粒分散體，製造多孔性銅薄膜之 例） 分散媒體改用二乙二醇與水之1 : 1混合物，以如同實 施例1之分散方法調製氧化銅微粒子分散體。煅燒環境氣 本紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ 297公瘦Ί " -34- (請先閲讀背面之注意事項再填寫本頁) 訂 1236931 A7 ________ B7 五、發明説明（31) 监改爲S ’煅燒溫度爲3 5 0 °C，爐燒爐爲密閉系統，锻燒爐 ，之溫度由室溫以1小時升溫至35(TC，達3 50t後於該溫度 (請先閲讀背面之注意事項再填寫本頁) 再加熱1小時锻燒。冷卻後取出載玻片作觀察，得厚5微 米、孔徑約0· 5微米之多孔性銅薄膜。又，該薄膜易於以膠 帶自載玻片剝離，該薄膜之體積電阻値爲5X 1 〇·5歐姆公分 〇 (實施例4 :調製氧化銅微粒分散體，製造銅薄膜之例） 經濟部智慧財產局員工消費合作社印製 混合氧化銅奈米粒子（粒徑1 〇至1 〇〇奈米，標稱平均粒 徑30奈米，CI化成（股）製）5克，聚乙二醇（平均分子量600 ’和光純藥工業（股）製）1克，及乙二醇）（和光純藥工業（股） 製）4克，以如同實施例1之條件得氧化銅微粒分散體。將 所得氧化銅微粒塗布於載玻片上成爲長5公分、寬1公分 、厚1〇微米。將上述載玻片送入煅燒爐內，爐內以真空泵 脫氣後，以流量1公升/分鐘之氫氣流通。煅燒爐以1小時 由室溫升溫至250°C，達250°C後再於該溫度加熱1小時作 處理。冷卻後確認載玻片上形成有厚8微米之均勻銅薄膜 。該薄膜與載玻片之粘合性高，以膠帶剝離試驗無法剝落 。該薄膜之體積電阻値低如1.5x 10·5歐姆公分。 .(實施例5至7 :調製氧化銅微粒分散體，製造銅薄膜之例） 混合氧化銅奈米粒子（粒徑10至100奈米，標稱平均粒 徑30奈米，CI化成（股）製）5克，乙二醇（和光純藥工業（股） 製）4.5克，及平均分子量各400、600、1〇〇〇之聚乙二醇（和 ^紙張尺度適用中國國家標準（CNS ) A4規4各i 210X 297公釐)~— -35- 1236931 A7 B7 五、發明説明（ (請先閱讀背面之注意事項再填寫本頁) 光純藥工業（股）製）〇·5克，以如同實施例丨之分散體條件得 氧化銅微粒分散體。如同實施例形成銅薄膜。所得銅薄膜 與載玻片之粘合性皆商’以膠剝離試驗均無法剝離。該等 薄膜之體積電阻値低如2至3χ 1(Τ5歐姆公分。 (實施例8 :調製氧化銅微粒分散體，製造銅薄膜之例） 混合氧化銅奈米粒子（粒徑1 0至1 0 0奈米，標稱平均粒 徑30奈米，CI化成（股）製）4克，水2克，及平均分子量 400之聚乙二醇（和光純藥工業（股）製）2克，以如同實施例1 之分散條件得氧化銅微粒分散體。如同實施例形成銅被膜 。所得銅被膜易於以膠帶從載玻片剝離，體積電阻値爲4χ 1 CT5歐姆公分。 (實施例9 :合成氧化亞銅微粒分散體，製造銅薄膜之例） . 於玻璃三口燒瓶內饋入醋酸銅（和光純藥工業（股）製）2·7 經濟部智慧財產局P'工消費合作社印製 克，純水0.9克，及二乙二醇9 0毫升。於油浴中升溫至 190°C，於該溫度持續加熱2小時。反應2小時後冷卻至室 溫，以日立工機（股）製之離心分離機將產物離心沈降。捨棄 上澄液中未反應之醋酸銅等。於離心分離沈澱物加1 00毫 升之二乙二醇，以超音波分散，以離心分離，於20,000G之 重力沈降粒徑大於1 0 0奈米之氧化亞銅粒子，餘留在上澄 液之100奈米以下之氧化亞銅再以離心分離，於3 5,000G之 重力沈降，得1 00奈米以下之氧化亞銅粒子沈澱物。所得 粒子一部份於載玻片上以8 5 °C真空乾燥後，用電子顯微鏡 本紙張尺度適用中國國家標準（CNS ) A4規格（210:<29?公釐） -36- 1236931 Α7 Β7 五、發明説明（ 觀測表面形態，係一次粒徑30至100奈米之氧化亞銅，平 均粒徑80奈米。以雷射散射法觀測之平均二次粒徑爲120 奈米。 對氧化亞銅粒子0.3克加聚乙二醇（平均分子量400，和 光純藥工業（股）製）0.12克，二乙二醇0.18克，經超音波分 散成氧化亞銅分散體。將所得氧化亞銅分散體塗布於載玻 片上成爲長5公分、寬1公分、厚30微米。將上述載玻片 送入煅燒爐內，爐內以真空泵脫氣後，以流量0.1公升/分 鐘之氫氣流通。煅燒爐由室溫以1小時升溫至300°C，達 300°C後，再於該溫度加熱處理1小時。冷卻後確認於載玻 片上形成有厚8微米之均勻銅薄膜。所得銅薄膜與載玻片 .之粘合性高，以膠帶剝離試驗無法剝離。該薄膜之體積電 阻率低如4χ 1(Τό歐姆公分。 (實施例10:合成氧化亞銅微粒分散體，製造銅薄膜之例（ 使用混合分散媒體之例）） 對實施例9所得之氧化亞銅粒子0.3克加聚乙二醇（平 均分子量400，和光純藥工業（股）製）0,12克，乙二醇〇.〇5 克，及乙醇0.13克，以超音波分散成氧化亞銅分散體。如 同實施例9於載玻片上塗布、煅燒，得厚9微米，體積電 阻率6.0X 1(Τ6歐姆公分之銅薄膜。所得銅薄膜與載玻片之 '粘合性高，以膠帶剝離試驗無法剝落。 (實施例1 1 :合成氧化亞銅微粒分散體，製造銅薄膜之例（ 本紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ 297公釐） 扣衣-- (請先閱讀背面之注意事項再填寫本頁) 訂 經濟部智慧財產局S工消費合作社印製 -37- 1236931 A7 _____B7 五、發明説明（ 作鈍性環境氣體及還原環境氣體之二煅燒之例）） (請先閱讀背面之注意事項再填寫本頁) 煅燒實施例9所得之氧化亞銅微粒分散體時，不直接 於3 0 0 °C作氫速原處理，而係先置載玻片於熱板上，熱板 全體以氮氣流通’熱板由室溫上升至2 5 0 °C，於2 5 0 °C煅燒 .1小時。冷卻後將預煅燒之上述載玻片移入煅燒爐，爐內以 真空泵充分排氣後，爐中以氫氣流通，於30(TC正式煅燒1 小時’得膜厚5微米之銅薄膜。銅薄膜之體積電阻値係極 低之3χ 1(Τδ歐姆公分。所得銅薄膜與載玻片之粘合性高， 以膠帶剝離試驗無法剝離。 (實施例1 2 :合成含糖醇之氧化亞銅微粒分散體，製造銅薄 膜之例 經濟部智慧財產局員工消費合作社印製 於實施例9所得粒徑100奈米以下之氧化亞銅粒子〇. 1 克加聚乙二醇（平均分子量400，和光純藥工業（股）製）〇·1克 * ，山梨糖醇0.1克，及乙二醇0.7克，以超音波分散得含氧 化亞銅10重量％之氧化亞銅分散體。分散後當時的分散體 中氧化亞銅之平均二次粒徑爲1 20奈米。超音波分散後， 該分散體靜置過夜，其中氧化亞銅之平均二次粒徑不變。 所得分散體用線條-間隙30微米之網印版（S〇N〇C〇M( 股）製）網印於聚醯亞胺膜上時印刷性良好。將上述載玻片送 入煅燒爐內，爐內以真空泵脫氣後，以流量1公升/分鐘之 氫氣流通，煅燒爐由室溫以1小時升溫至250°C，達250°C 後再於該溫度加熱處理1小時。冷卻後取出聚醯亞胺膜， 以顯微鏡觀察其表面，可確認形成有銅配線而無斷線。 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） -38- 1236931 A7 _B7 五、發明説明（ (請先閱讀背面之注意事項再填寫本頁) (實施例1 3 :合成含糖醇之氧化亞銅微粒分散體，製造銅薄 膜之例） 所用糖醇爲赤蘚糖以外，如同實施例1 2調製氧化亞銅 分散體，超音波分散後靜置過夜，分散體中氧化亞銅之平 均二次粒徑不變，仍爲1 20奈米。該分散體如同實施例i 2 以線條-間隙30微米之網印版網印於聚醯亞胺上時印刷性良 好。如同實施例1 2作加熱處理，冷卻後取出聚醯亞胺膜， 以顯微鏡觀察其表面，可確認形成有銅配線而無斷線。 (實施例14:合成合金屬粉之氧化銅微粒分散體，製造銅薄 膜之例） 經濟部智慧財產局8工消費合作社印製 氧化銅微粒（粒徑10至100奈米，標稱平均粒徑30奈 米，CI(股）製5克，乙二醇（和光純藥工業（股）製）4克，聚 乙二醇（平均分子量600)，及銀粒子（平均粒徑2.5微米）， Sigma Aldrich公司製）0.5克以如同實施例1之方法分散， 得含銀粒子之氧化銅微粒分散體，如同實施例1煅燒。所 得含銀粒子之銅薄膜，其體積電阻値爲7x1 0·5歐姆公分。 所得薄膜比不含銀柱子之銅薄膜之銅薄膜抗氧化性強。又 ，所得薄膜與載玻片之粘合物高，以膠帶剝離認驗不剝落 (實施例1 5 :合成含環氧樹脂之氧化銅微粒分散體’製造 .銅薄膜之例） 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） -39- 1236931 A7 , _ B7 五、發明説明（ (請先閱讀背面之注意事項再填寫本頁) 氧化銅微粒（粒徑10至100奈米，標稱平均粒徑30奈 *米，CI(股）製）5克，乙二醇（和光純藥工業（股）製）4.5克，1 ’ 4-丁二醇二環氧內醚〇·1克，及聚乙二醇（分子量600)0.4 克如同實施例1分散。分散後加入環氧硬化劑微表化硬化 齊(J(N〇VACURE HX-3088，旭化成 EPOXY(.股）製 0.03 克，以 刮刀攪混後，如同實施例1煅燒，測定體積電阻率，爲7 X 1 (T5歐姆公分。所得銅薄膜與載玻片間之粘合性遠高於不 含環氧樹脂的分散體。 (實施例1 6 :合成含聚醯亞胺樹脂的氧化銅粒子分散體，製 造銅薄膜之例） 經濟部智慧財產局員工消費合作社印製 雙（4-胺基苯基）醚10.0克及均苯四酸酐10.9克溶解於 N-甲基吡略烷酮（NMP)IOO克，於室溫攪拌1小時，得聚醯 胺酸之NMP溶液。於該聚醯胺酸溶液2克加氧化銅粒子（粒 徑10至100奈米，標稱平均粒徑30奈米，CI化成（股）製）5 克’及乙二醇（和光純藥工業（股）製）3克，如同實施例1分 散。將該分散體塗布於切成3公分X 3公分之聚醯亞胺膜（ TORAY · DuPont公司製KAPTON膜，厚50微米）上，於氬 環境氣體中以3 5 0 °C還原處理1小時，於聚醯亞胺膜上形成 含聚醯亞胺之銅薄膜。銅薄膜具導電性，體積電阻率爲9x .1 cr5歐姆公分。所得銅薄膜密合性遠高於不含聚醯胺酸而锻 燒於聚醯亞胺膜上之薄膜。 (實施例17 :合成含還原劑之氧化銅微粒分散體，製造多孔 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） ' -40- 1236931 A7 __ B7 ____ 五、發明説明（3i 性銅薄膜之例） (請先閱讀背面之注意事項再填寫本頁) 氧化銅奈米粒子（粒徑10至100奈米，標稱平均粒徑 30奈米，CI化成（股）製）5克，二乙二醇（和光純藥工業（股） 製）4.5克，及丙醛（和光純藥工業（股）製）〇.5克，如同實施 例i分散得氧化銅微粒分散體。所得分散體如同實施例塗 布於載玻片上，煅燒爐中，流通以流量〇·丨公升/分鐘之氬 氣由室溫以1小時升溫至350°C，達350°C後再於該溫度加 .熱處理1小時。所得銅薄膜之體積電阻値低如3x 10_5歐姆 公分。 (實施例8 :於矽晶圓製造銅薄膜之例） 經濟部智慧財產局員工消費合作社印製 氧化銅奈米粒子（粒徑10至100奈米，標稱平均粒徑 30奈米，CI化成（股）製）5克，乙二醇（和光純藥工業（股）製） 4·5克，及聚乙二醇（和光純藥工業（股）製）0.5克，如同實施 例1分散，得氧化銅微粒分散體。預先用信越化學（股）製表 面處理劑（LS-3 150)作表面處理之5吋矽晶圓，安置於MIKA SA(股）製旋塗機（1H-D7型）將上述分散體滴於矽晶圓上，以 lOOOppm預旋10秒後以300rpm旋塗30秒。塗布後之砂晶 圓如同實施例1煅燒。矽晶圓上所得之銅薄膜厚0.6微米， 體積電阻値低如6x 1(Τ6歐姆公分。 (實施例19 :調製氧化亞銅分散體，製造銅薄膜之例） 於純水60毫升加無水醋酸銅（和光純藥工業（股）製）8克 ，於25°C攪拌下加肼單水合物（和光純藥工業（股）製）作還原 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） -41 - 1236931 A7 ____ B7 五、發明説明（3》 (請先閱讀背面之注意事項再填寫本頁) 反應，得一次粒徑1 〇至3 0奈米之氧化亞銅微粒。於該氧 化亞銅微粒0.5克加二乙二醇0.1克及聚乙二醇（平均分子 量200，和光純藥工業（股）製）0.4克，以超音波分散調製氧 . 化亞銅分散體。將該分散體塗布於載玻片上成爲長5公分 、寬1公分、厚20微米。將上述載玻片送入煅燒，爐內以 真空泵脫氣後，並再以氬氣取代。煅燒爐由室溫以1小時 升溫至3 50°C，達350°C後再於該溫度加熱處理1小時。冷 卻後得厚7微米、體積電阻率4.Ox 1(Τ6歐姆公分之銅薄膜 。所得薄膜與載玻片之粘合性高，以膠帶剝離試驗無法剝 落。 (比較例1 :金屬氧化物微粒之粒徑） 平均粒徑2.8微米之氧化銅粉末（和光純藥工業（股）製）5 '克及二乙二醇5克，如同實施例1分散處理得氧化銅分散 體，如同實施例1於載玻片上煅燒成分散體膜。載玻片上 之金屬銅表面多有微細龜裂，係不完整之銅薄膜。以SEM 觀察知銅粉末間粒子熔合不足。 經濟部智慧財產局員工消費合作社印製 (比較例2 :金屬氧化物微粒之粒徑） 平均粒徑2.8微米之氧化銅粉末（和光純藥工業（股）製）5 克，二乙二醇4.5克，及聚乙二醇（平均分子量600)0.5克如 同實施例1分散處理調製氧化銅分散體，如同實施例1於 載玻片上煅燒成分散體塗膜。載玻片上之金屬銅表面多有 微細龜裂，係不完整之銅薄膜。以SEM觀察知銅粉末間粒 本紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ 297公釐） -42- 1236931 A7 B7 五、發明説明（ 子熔合不足。 .產業上之利用可能性 依本發明可用廉價金屬氧化物爲原料，以相對低溫處 理’於基板上形成金屬薄膜。控制金屬氧化物分散體在基 板上之塗布厚度，即可任意控制金屬薄膜之膜厚。又，可 .用噴墨塗布法直描形成配線，以該法可略去習知配線形成 製程所需之光微影及蝕刻過程，可節省資源、低成本形成 配線。所得金屬薄膜適用於電極、配線、電路等之金屬配 線材料或導電材料之用途。所得具孔徑1微米以下，均句 微細多孔結構之多孔性金屬薄膜適用於例如，觸媒用載體， 、無機濾材、導電材料、導熱材料等用途，以及必須大面 積之電極等用途。 . 裝-- (請先閱讀背面之注意事項再填寫本頁) 訂 經濟部智慧財產局員工消費合作社印製 本紙張尺度適用中國國家標準（CNS ) A4規格（210X 297公釐） -43--28- 1236931 Α7 Β7 Intellectual Property Bureau of the Ministry of Economic Affairs (printed by the Industrial and Consumer Cooperatives) 5. Description of the invention (methyl methyldiethoxysilane, 3-methylpropyltrimethoxysilane, ^ glycidoxypropane Dimethyl methacrylate base, 3-hydroxypropoxypropyl methyldimethoxy stone wick, 3-methacrylic acid methoxy propyl trimethoxy ash, 3-methacrylic acid Oxypropylmethyldimethoxy sand ash, hexamethyl dimethyl sand ash, ammonia, ethyl ethyl acetate, diisopropoxy aluminum, ginseng (ethyl ethyl acetate) aluminum, bis (ethyl ethyl acetate) Ethyl acetate) aluminum monoethylacetate, ginseng (ethylacetate) aluminum, etc. When coating these adhesion promoters, if necessary, other additives can be added and diluted with a solvent. Treatment of adhesion promoters A known method can be used for this purpose. In order to improve the adhesion with the organic substrate, a method of dipping the organic substrate in an alkaline aqueous solution and heating it can also be used. For example, the polyimide resin can be about 5 mM potassium hydroxide The solution is treated for about 5 minutes, and the sulfonimide ring is cleaved to generate a carboxyl group to give a nail anchor effect. Using the metal oxide component of the present invention When a metal thin film is formed on a substrate, a metal oxide dispersion is first coated on the substrate. The coating method may be a general method used for coating the dispersion on the substrate, such as a screen printing method, a dip coating method, a spray coating method, Spin coating method, inkjet method, etc. When coating the dispersion on a substrate, the coating thickness is preferably 0.1 to 100 microns, and more preferably 1 to 30 microns. After the dispersion is coated on the substrate, the substrate is sufficient to oxidize the metal The temperature at which the material is reduced to metal is heat treated to form a metal thin film on the substrate. When the obtained metal thin film is easily oxidized, it is better to perform heat treatment in a non-oxidizing ambient gas. It is difficult to use metal oxide only in the metal oxide dispersion When reducing reducing agents (reducing agents other than polyols, polyether compounds, additional polyols, and polyether compounds), it is better to calcine in a reducing ambient gas. (Please read the precautions on the back before filling in this Page) This paper size applies to Chinese National Standard (CNS) A4 specification (210X 297 mm) -29-1236931 • A7 _______ B7 V. Description of invention ((Please read the Please fill in this page again.) After calcination in inert ambient gas, the metal thin film obtained by subsequent calcination in reducing ambient gas is better because of higher density. Non-oxidizing ambient gas does not contain oxygen, etc. The environment gas of oxidizing gas includes inert environment gas and reducing environment gas. Inert environment gas refers to an environment gas filled with inert gases such as argon, helium, neon, nitrogen, etc. Reducing environment gas refers to hydrogen, Monoxide & ^ and other ambient gases in the existence of the original gas. These gases can be filled in the calciner to form a closed system for calcination, or the calciner can be used as a circulation system • 'Circulate these gases. In a non-oxidizing environment When calcining in gas, the calcining furnace can be temporarily evacuated to remove oxygen and replaced with non-oxidizing gas. Calcination can be performed in a pressurized ambient gas or in a reduced-pressure ambient gas. In these reduction treatments, the heat treatment temperature is preferably 50 ° C to 500 ° C, 80 ° C to 40 ° C (more preferably, TC to 100 ° C, and 3 to 50 ° C). The metal oxidation of the present invention Polyol compounds and / or polyether compounds, which are essential components of the dispersion, can be incinerated (or decomposed) at such a relatively low temperature. Metal oxides can be reduced at temperatures below 50 ° C, etc., and the storage stability of metal oxide dispersions is stable The property tends to deteriorate. When it is higher than 500 ° C, the heat resistance of most organic substrates cannot be used on organic substrates, so they are not good. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs ^ Heat treatment The time required is affected by the type of metal oxide, the heating ambient gas, the temperature of the heat treatment, and the shape and size of the dispersion to be heat treated. The metal oxide is copper oxide, and the coating film is at the micron level, and the hydrogen is not diluted. It can be directly used as a reducing gas, and the heat treatment temperature can be set between 2000 ° C and 300 ° C in 1 to 2 minutes. For the same metal oxide, the smaller the particle diameter is, the easier the reduction is than the larger particle diameter, so the particle diameter Big hour or Calcined in reducing ambient gas, the particle size is small or only the size of the paper is compliant with China National Standard (CNS) A4 specification (210X297 mm) -30-1236931 A7 B7 V. Description of the invention (2) Calcination in nature ambient gas It can be reduced. At this time, it is calcined in an inert ambient gas, and it is possible to form a practically non-problematic metal film. The metal film 1 obtained by calcining the metal oxide dispersion of the present invention has a particle size of less than 2 0 0 Nano-sized metal oxide particles are used as raw materials, and the microstructure is a structure of metal particles with a primary particle size of less than 200 nanometers obtained by reduction of the raw material metal oxide particles. More specifically, the primary particle size is less than 200 nanometers. The metal particles of rice are fused with each other to form particles. The structure of contact between particles and fused to form a thin film. This can be confirmed by observing the calcined metal film with an electron microscope. The size of metal particles formed by the fusion of metal particles obtained by reduction of metal oxide particles, It varies with the heat treatment environment gas, temperature, and processing time. The high temperature and long time heat treatment will make the metal particles larger. Also, Heating in a reducing ambient gas tends to increase the size of the metal particles. The larger the metal particles, the smaller and less porous structure between the metal particles and the densely stacked metal particles, the closer the conductivity of the metal film is to that of the metal body. Alas, it is more suitable as a conductive film. As described below, the structure of the metal film obtained by calcining the metal oxide dispersion varies with the content of the polyether compound in the metal oxide dispersion. The content of the polyether compound accounts for the total of the metal oxide dispersion. Weight 0.1 to 70% by weight A metal thin film calcined by a metal oxide dispersion. Metal particles are densely stacked on each other, and the volume resistance is close to that of a metal body. Therefore, it is suitable for, for example, low volume resistance in the field of construction. Wiring materials and connection materials required. On the other hand, the content of polyether compounds accounts for the total metal oxide dispersion. The paper size applies to China National Standard (CNS) A4 (210X297 mm) ~--31-( (Please read the notes on the back before filling out this page)-Binding and printing Printed by the Consumer Consumption Cooperative of the Intellectual Property Bureau of the Ministry of Economy 1236931 A7 ___B7 Description (j weight less than 0.1% by weight of the metal oxide dispersion obtained by calcination of the metal thin film due to a porous structure having a large surface area, suitable for use electrodes. With the manufacturing method described in this post (please read the precautions on the back before filling this page), porous metal films with a pore diameter of 1 micron or less can be manufactured. The metal film manufacturing method of the present invention is to reduce metal oxide particles to produce metal particles. The method of obtaining a metal thin film by fusing in between does not require pressure because of the spontaneous fusing attraction between the particles generated by reduction. In addition, as mentioned above, the primary particle diameter of the metal oxide fine particles is less than 200 nm, which is very small, and the polyether compound and the polyol itself have reducing properties, and the metal particles should be susceptible to spontaneous fusion. The polyol or polyether compound is calcined at a relatively low temperature. Because of its oxidation, decomposition, volatilization, and the presence of such insulating components in the metal film, it is not easy to remain. Therefore, the volume resistance of the metal film is low. Further, as described above, by adjusting the content of the polyether compound in the metal oxide dispersion, a porous metal film is easily obtained. By controlling the coating thickness of the metal oxide dispersion on the substrate, the film thickness of the obtained metal thin film can be arbitrarily controlled, especially for the advantages of easy formation of the extremely thin metal layer required for forming fine circuits, and is particularly suitable for adhesive-backed metal foil And other uses. When the metal oxide dispersion containing metal powder is printed by the Employee Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, the metal thin film produced by the reduction of metal oxide particles between metal powders is calcined. Therefore, the metal component of the metal thin film obtained in the present invention includes a metal obtained by reduction of a metal oxide, and a metal of added metal powder. Metal oxide reduction • The metal obtained can be the same or different from the metal powder. Metals that can constitute a metal film include, for example, gold, silver, copper, palladium, platinum, nickel, chromium, aluminum, tin, zinc, titanium, tungsten, tantalum, barium, germanium, ruthenium, bismuth, iridium, cobalt, indium, The size of the iron paper is applicable to the Chinese National Standard (CNS) A4 specification (210X 297 mm) — -32- 1236931 A7 B7 'V. Description of the invention (, lead, metal film contains at least one of these metals. Metal of the invention The thin film manufacturing method is a method of generating metal particles at a relatively low-temperature calcination site, and fusing the particles to produce a metal thin film. The raw materials used are not expensive metal particles, but are cheap metal oxides, so they can be manufactured cheaply. Advantages of metal films. In addition, metal oxide particles do not need to be dispersed in special media such as crystalline polymers (which need to be pyrolyzed), so they can be formed by heating at a relatively low temperature below 500 ° C. Therefore, It has the advantage of low process cost. In other words, the manufacturing method of the metal thin film of the present invention is a method of manufacturing a metal thin film by using a low-cost raw material and a low-temperature calcination process. The following examples illustrate the present invention in detail, but the present invention is not limited to this. The primary particle diameter of the copper oxide particles and the surface morphology of the metal film obtained by the calcination are made by a scanning electron microscope (S -47 0 0) Measured by observing the surface. The average secondary particle diameter of the metal oxide in the metal oxide dispersion is measured using a laser scattering particle size meter (LA-920) manufactured by Horiba. The volume of the obtained metal film The resistivity is determined by a low-resistivity meter (LOWRESTER GP (manufactured by Mitsubishi Chemical Corporation)) using the four-short needle method. (Example 1: Example of preparing a copper oxide particle dispersion and producing a porous copper film) 5 grams of ethylene glycol is added to copper oxide nano particles (particle size 10 to 100 nanometers' nominal average particle size 30 nanometers, manufactured by CI Chemicals Co., Ltd.) 5 grams. Chinese national standards ( CNS) A4 size (210X 297mm) (Please read the notes on the back before filling out this page)-Packing. Order printed by the Goods and Consumers Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs -33- 1236931 Employee Consumption of the Intellectual Property Bureau of the Ministry of Economic Affairs Co-operative print A 7 _ B7 V. Description of the invention (3 () KEYENS (shares) agitation defoamer (HM-5 00) in the stirring mode for 10 minutes, defoaming mode for 5 minutes under the conditions of dispersion treatment to obtain copper oxide particles dispersion The obtained copper oxide fine particle dispersion was coated on a glass slide to become 2 cm in length, 1 cm in width, and 20 microns in thickness. The above glass slide was sent to a calcining furnace, and the furnace was degassed with a vacuum pump at 1 liter / minute. The flow of hydrogen flows. The temperature of the calcining furnace is increased from room temperature to 250 ° C in 1 hour, and then heated at this temperature for 1 hour. After cooling, the glass slide is taken out and inspected. The thickness of the obtained copper film is 4 Porous film with a diameter of about 0.3 microns and a pore size of about 0.3 microns. This film is easily peeled off from a glass slide with an adhesive tape, and the volume resistance 値 of the film is 5 × 1 (Γ5 ohm cm. (Example 2: Example of preparing a copper oxide particle dispersion to produce a porous copper film) The dispersion medium is changed to B The diol was prepared by dispersing the copper oxide microparticle dispersion in the same manner as in Example 1. The calcination temperature was changed to 200 ° C except for hydrogen calcination of the copper oxide dispersion as in Example 1. The film was easily peeled from a glass slide with an adhesive tape. The volume resistance of the film is 6 × 1 (T5 ohm cm). After cooling, the glass slide is taken out for observation, and a porous copper film having a porous structure with a thickness of 4 micrometers and a pore size of about 0.2 micrometers is formed. (Example 3: Example of preparing copper oxide fine particle dispersion and producing porous copper film) The dispersion medium was changed to a 1: 1 mixture of diethylene glycol and water, and the copper oxide fine particle dispersion was prepared in the same manner as in Example 1. The calcining environment The size of the paper is applicable to the Chinese National Standard (CNS) Α4 specification (210 × 297 male thin Ί " -34- (Please read the precautions on the back before filling this page) Order 1236931 A7 ________ B7 V. Description of the invention 31) Supervised to S 'calcination temperature is 3 50 ° C, the furnace is a closed system, the temperature of the forging furnace is increased from room temperature to 35 (TC, 3 to 50 t after this temperature (please Read the precautions on the back before filling in this page.) Then heat for 1 hour. After cooling, take out the glass slide for observation, and obtain a porous copper film with a thickness of 5 micrometers and a pore size of about 0.5 micrometers. This film is easy to use. The tape was peeled from the glass slide, and the volume resistance of the film was 5 × 10.5 ohm cm. (Example 4: Example of preparing copper oxide particle dispersion and manufacturing copper film) Printed by the Consumer Cooperative of Intellectual Property Bureau, Ministry of Economic Affairs Mixed copper oxide nano particles (particle size 10 to 100 nanometers, nominal average particle size 30 nanometers, manufactured by CI Kasei Co., Ltd.) 5 g, polyethylene glycol (average molecular weight 600 ', Wako Pure Chemical Industries, Ltd.) 1 g of ethylene glycol, and 4 g of ethylene glycol) (made by Wako Pure Chemical Industries, Ltd.), and a copper oxide particle dispersion was obtained under the same conditions as in Example 1. The obtained copper oxide particles were coated on a glass slide. It is 5 cm long, 1 cm wide, and 10 micrometers thick. Inside the furnace, the furnace is degassed with a vacuum pump and then circulated with hydrogen at a flow rate of 1 liter / minute. The calcining furnace is heated from room temperature to 250 ° C in 1 hour, and then heated at this temperature for 1 hour for treatment. After cooling, it was confirmed that a uniform copper film with a thickness of 8 micrometers was formed on the glass slide. The film had high adhesion to the glass slide and could not be peeled off by the tape peel test. The volume resistance of the film was as low as 1.5x 10 · 5 ohm cm (Examples 5 to 7: Examples of preparing copper oxide fine particle dispersions and manufacturing copper thin films) Mixed copper oxide nano particles (particle size 10 to 100 nm, nominal average particle size 30 nm, CI formed into ) 5 grams, 4.5 grams of ethylene glycol (Wako Pure Chemical Industries, Ltd.) 4.5 grams, and polyethylene glycols with average molecular weights of 400, 600, and 1,000 (and ^ paper standards apply Chinese national standards (CNS ) A4 rule 4 i 210X 297 mm) ~--35- 1236931 A7 B7 V. Description of invention ((Please read the precautions on the back before filling this page) Optical Pure Pharmaceutical Industry Co., Ltd. 0.5 grams, A dispersion of copper oxide particles was obtained under the same dispersion conditions as in Example 丨. A copper thin film was formed as in the examples. The adhesion between the obtained copper thin film and the glass slide was both quotable, and neither could be peeled off by the glue peel test. The volume resistance of these films is as low as 2 to 3 × 1 (T5 ohm cm.) (Example 8: Example of preparing copper oxide particle dispersion to produce a copper film) Mixed copper oxide nano particles (particle size 10 to 10) 0 nanometers, nominal average particle size of 30 nanometers, 4 grams of CI Kasei Co., Ltd., 2 grams of water, and 2 grams of polyethylene glycol (Wako Pure Chemical Industries, Ltd.) with an average molecular weight of 400 grams. A copper oxide particle dispersion was obtained under the same dispersion conditions as in Example 1. A copper coating was formed as in the example. The obtained copper coating was easily peeled from the glass slide with a tape, and the volume resistance 値 was 4 × 1 CT5 ohm cm. (Example 9: Synthetic oxidation Example of manufacturing copper thin film dispersion, copper film). Feed glass acetate (made by Wako Pure Chemical Industries, Ltd.) into a glass three-necked flask. 2 · 7 printed by P'Industrial and Cooperative Cooperative of Intellectual Property Bureau, Ministry of Economic Affairs. 0.9 g of water and 90 ml of diethylene glycol. The temperature was raised to 190 ° C in an oil bath, and the temperature was continuously heated for 2 hours. After 2 hours of reaction, it was cooled to room temperature and centrifuged by Hitachi Koki Co., Ltd. The separator settles the product by centrifugation. Discard unreacted copper acetate in the supernatant Etc. Add 100 ml of diethylene glycol to the centrifugal separation sediment, disperse it with ultrasound, centrifuge it, and settle the cuprous oxide particles with a particle size greater than 100 nm at a gravity of 20,000 G, leaving it on The cuprous oxide below 100 nanometers in the clear solution is centrifuged and settled at a gravity of 3 5,000 G to obtain a precipitate of cuprous oxide particles below 100 nanometers. A part of the obtained particles is placed on a glass slide at 8 5 After vacuum drying at ° C, the paper size shall be in accordance with Chinese National Standard (CNS) A4 specification (210: < 29? Mm) -36- 1236931 Α7 Β7 using an electron microscope. V. Description of the invention (Observation of surface morphology, primary particle size Cuprous oxide from 30 to 100 nanometers, with an average particle size of 80 nanometers. The average secondary particle diameter as measured by laser scattering method is 120 nanometers. 0.3 g of cuprous oxide particles with polyethylene glycol (average molecular weight 400) , Manufactured by Wako Pure Chemical Industries, Ltd. (0.12 g) and diethylene glycol (0.18 g) by ultrasonic dispersion into a cuprous oxide dispersion. The obtained cuprous oxide dispersion was coated on a glass slide to be 5 cm long and 1 wide Cm, 30 microns thick. Send the above slide into the calciner Inside, the furnace is degassed by a vacuum pump and then circulated with hydrogen at a flow rate of 0.1 liters / minute. The calcining furnace is heated from room temperature to 300 ° C for 1 hour, and reaches 300 ° C, and then heat-treated at this temperature for 1 hour. Cooling It was confirmed that a uniform copper film with a thickness of 8 microns was formed on the glass slide. The obtained copper film had a high adhesion to the glass slide and could not be peeled off by a tape peeling test. The volume resistivity of the film was as low as 4 × 1 (Τόohm (Example 10: Example of synthesizing a cuprous oxide microparticle dispersion and manufacturing a copper film (example using a mixed dispersion medium)) 0.3 g of the cuprous oxide particles obtained in Example 9 were added with polyethylene glycol (average molecular weight 400) , Manufactured by Wako Pure Chemical Industries, Ltd. (0,12 g), 0.05 g of ethylene glycol, and 0.13 g of ethanol, were dispersed ultrasonically into a cuprous oxide dispersion. The copper film was coated and calcined as in Example 9 to obtain a thickness of 9 micrometers and a volume resistivity of 6.0X 1 (T6 ohm cm copper film. The obtained copper film had a high adhesion to the glass slide, which was not possible with a tape peel test. Exfoliation. (Example 11: Example of synthesizing cuprous oxide microparticle dispersion and manufacturing copper film. (This paper size applies the Chinese National Standard (CNS) A4 specification (210 × 297 mm)) Button clothing-(Please read the back Please fill in this page before ordering) Order printed by S Industrial Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs-37- 1236931 A7 _____B7 V. Description of the invention (as an example of calcination of inert ambient gas and reducing ambient gas) (Please read first Note on the back, please fill in this page again.) When calcining the cuprous oxide microparticle dispersion obtained in Example 9, do not directly treat hydrogen at 300 ° C, but first place the slide glass on a hot plate, heat The entire plate is circulated with nitrogen. The hot plate is raised from room temperature to 250 ° C and calcined at 250 ° C for 1 hour. After cooling, the pre-calcined slides are moved into a calciner, and the furnace is fully discharged by a vacuum pump. After the gas is passed, the furnace is circulated with hydrogen gas at 30 (TC positive Calcined for 1 hour to obtain a copper film with a thickness of 5 microns. The volume resistance of the copper film is extremely low 3 × 1 (Tδ ohm cm). The obtained copper film has high adhesion to a glass slide, and cannot be peeled off by a tape peeling test. (Example 12: Example of synthesizing a cuprous oxide microparticle dispersion containing sugar alcohol and manufacturing a copper film) The employee cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs printed a cuprous oxide particle having a particle diameter of 100 nm or less obtained in Example 9. 1 g of polyethylene glycol (average molecular weight 400, manufactured by Wako Pure Chemical Industries, Ltd.) 0.1 g *, 0.1 g of sorbitol, and 0.7 g of ethylene glycol, dispersed by ultrasound to obtain cuprous oxide 10% by weight cuprous oxide dispersion. The average secondary particle diameter of cuprous oxide in the dispersion at the time after dispersion was 120 nm. After ultrasonic dispersion, the dispersion was allowed to stand overnight, where the average of cuprous oxide was The secondary particle size does not change. The obtained dispersion was screen-printed on a polyimide film with a screen-printing plate (made by SONO COM (strand)) with a line-gap of 30 micrometers. The printability was good. The glass slide is sent into the calcining furnace, which is degassed by a vacuum pump, and the flow rate is 1 Liter / minute of hydrogen flow, the calcining furnace was heated from room temperature to 250 ° C for 1 hour, and then heated at this temperature for 1 hour. After cooling, the polyimide film was taken out, and its surface was observed with a microscope. It can be confirmed that the copper wiring is formed without disconnection. This paper size applies to Chinese National Standard (CNS) A4 specification (210X 297 mm) -38- 1236931 A7 _B7 V. Description of the invention ((Please read the precautions on the back before filling This page) (Example 13: Example of synthesizing a cuprous oxide microparticle dispersion containing sugar alcohol and producing a copper thin film) The sugar alcohol used was other than erythrose, and the cuprous oxide dispersion was prepared in the same manner as in Example 12 and the ultrasonic wave was prepared. After the dispersion was left to stand overnight, the average secondary particle diameter of the cuprous oxide in the dispersion was unchanged, still being 120 nm. This dispersion had good printability when screen-printed on a polyimide with a screen-plate having a line-gap of 30 m as in Example i 2. Heat treatment was performed in the same manner as in Example 12. After cooling, the polyimide film was taken out and the surface was observed under a microscope. It was confirmed that copper wiring was formed without disconnection. (Example 14: Example of synthesizing copper oxide particle dispersion of synthetic metal powder and manufacturing copper thin film) Printed copper oxide particles (particle size 10 to 100 nm, nominal average particle size) 30 nanometers, 5 grams of CI (stock), 4 grams of ethylene glycol (made by Wako Pure Chemical Industries, Ltd.), polyethylene glycol (average molecular weight 600), and silver particles (average particle size 2.5 microns), Sigma 0.5 g of Aldrich) was dispersed in the same manner as in Example 1 to obtain a dispersion of copper oxide particles containing silver particles, which was calcined as in Example 1. The obtained copper film containing silver particles had a volume resistance 値 of 7 × 1 0 · 5 ohm cm. The obtained film is more resistant to oxidation than a copper film having no silver pillars. In addition, the adhesion between the obtained film and the glass slide is high, and it is not peeled off by peeling off the tape for verification (Example 15: Synthetic copper oxide microparticle dispersion containing epoxy resin 'made by example of copper film). China National Standard (CNS) A4 specification (210X 297 mm) -39- 1236931 A7, _ B7 V. Description of the invention ((Please read the precautions on the back before filling this page) Copper oxide particles (particle size 10 to 100 nanometers) Rice, nominal average particle size of 30 nanometers * meters, 5 grams of CI (stock), 4.5 grams of ethylene glycol (made by Wako Pure Chemical Industries, Ltd.), 1 '4-butanediol diepoxylactone. 1 gram and 0.4 gram of polyethylene glycol (molecular weight 600) were dispersed as in Example 1. After the dispersion, an epoxy hardener was added for micro-surface hardening (J (NVACVACURE HX-3088, manufactured by Asahi Kasei EPOXY Co., Ltd.) 0.03 g, after mixing with a spatula, calcined as in Example 1, and measuring the volume resistivity, it was 7 X 1 (T5 ohm cm). The adhesion between the obtained copper film and the glass slide was much higher than the dispersion without epoxy resin. (Example 16: Example of synthesizing a copper oxide particle dispersion containing a polyimide resin and manufacturing a copper thin film) Economy 10.0 grams of bis (4-aminophenyl) ether and 10.9 grams of pyromellitic anhydride printed by the Consumer Cooperatives of the Ministry of Intellectual Property Bureau were dissolved in 100 grams of N-methylpyrrolidone (NMP) and stirred at room temperature for 1 hour NMP solution of polyamic acid was obtained. 2 grams of polyamic acid solution was added with copper oxide particles (particle size 10 to 100 nm, nominal average particle size 30 nm, CI Chemical Co., Ltd.) 5 g 'And 3 g of ethylene glycol (Wako Pure Chemical Industries, Ltd.) was dispersed as in Example 1. This dispersion was applied to a polyimide film cut into 3 cm X 3 cm (KAPTON manufactured by TORAY DuPont) Film, 50 micrometers thick), reduction treatment in argon ambient gas at 3 50 ° C for 1 hour to form a polyimide-containing copper film on the polyimide film. The copper film has conductivity and volume resistivity It is 9x .1 cr5 ohm centimeters. The adhesion of the obtained copper film is much higher than that of a film that is calcined on a polyimide film without polyamic acid. (Example 17: Dispersion of copper oxide particles containing a reducing agent) The size of the paper is made of porous paper. The size of the paper is applicable to the Chinese National Standard (CNS) A4 (210X297 mm) '-40- 1236931 A7 __ B7 ____ 、 Explanation of the invention (example of 3i copper film) (Please read the precautions on the back before filling this page) Copper oxide nano particles (particle size 10 to 100 nm, nominal average particle size 30 nm, CI formed into ( 5 g of diethylene glycol), 4.5 g of diethylene glycol (Wako Pure Chemical Industries, Ltd.) and 0.5 g of propionaldehyde (Wako Pure Chemical Industries, Ltd.) 0.5 g of copper oxide were dispersed as in Example i Microparticle dispersion. The obtained dispersion was coated on a glass slide as in the example, and in a calcining furnace, argon gas was flowed at a flow rate of 0.1 liters / minute from room temperature to 350 ° C in 1 hour, and then reached 350 ° C. Add heat treatment at this temperature for 1 hour. The volume resistance of the obtained copper film is as low as 3 x 10-5 ohm cm. (Example 8: Example of manufacturing a copper film on a silicon wafer) Printed copper oxide nano particles (particle size 10 to 100 nm, nominal average particle size 30 nm, CI chemical conversion) 5 g, manufactured by Wako Pure Chemical Industries, Ltd., 4.5 g, and 0.5 g, polyethylene glycol (made by Wako Pure Chemical Industries, Ltd.), and dispersed as in Example 1, A copper oxide particle dispersion was obtained. A 5-inch silicon wafer with a surface treatment agent (LS-3 150) made by Shin-Etsu Chemical Co., Ltd. as a surface treatment was placed in a spin-coater (type 1H-D7) made by MIKA SA. On a silicon wafer, pre-spin at 1000 ppm for 10 seconds and spin-coat at 300 rpm for 30 seconds. The sand crystal circle after coating was calcined as in Example 1. The copper film obtained on the silicon wafer is 0.6 micrometers thick and has a volume resistance as low as 6x 1 (T6 ohm cm. (Example 19: Example of preparing a cuprous oxide dispersion to produce a copper film). Add 60 mL of pure water to anhydrous acetic acid. 8 grams of copper (made by Wako Pure Chemical Industries, Ltd.), added with hydrazine monohydrate (made by Wako Pure Chemical Industries, Ltd.) for stirring at 25 ° C. This paper is sized to Chinese National Standard (CNS) A4 specifications ( 210X 297mm) -41-1236931 A7 ____ B7 V. Description of the invention (3) (Please read the precautions on the back before filling out this page) The reaction results in a cuprous oxide particle with a particle size of 10 to 30 nm. . 0.5 g of cuprous oxide particles plus 0.1 g of diethylene glycol and 0.4 g of polyethylene glycol (average molecular weight 200, manufactured by Wako Pure Chemical Industries, Ltd.), using ultrasonic dispersion to modulate oxygen. Cuprous dispersion The dispersion was coated on a glass slide to be 5 cm in length, 1 cm in width, and 20 microns in thickness. The above glass slide was sent to a calcination, degassed by a vacuum pump in the furnace, and replaced with argon. The calcination furnace was The room temperature is raised to 3 50 ° C in 1 hour. After reaching 350 ° C, it is added at this temperature. Treat for 1 hour. After cooling, a copper film with a thickness of 7 micrometers and a volume resistivity of 4.Ox 1 (T6 ohm cm) is obtained. The obtained film has high adhesion to the glass slide and cannot be peeled off by a tape peeling test. (Comparative Example 1: Particle size of metal oxide particles) Copper oxide powder (manufactured by Wako Pure Chemical Industries, Ltd.) with an average particle size of 2.8 micrometers and 5 g of diethylene glycol, and the dispersion was treated as in Example 1 to obtain a copper oxide dispersion. The dispersion film was calcined on a glass slide as in Example 1. The metallic copper surface on the glass slide was mostly cracked, which was an incomplete copper thin film. SEM observation revealed that the particle fusion between the copper powders was insufficient. Bureau of Intellectual Property, Ministry of Economic Affairs Printed by an employee consumer cooperative (Comparative Example 2: Particle size of metal oxide particles) 5 g of copper oxide powder (manufactured by Wako Pure Chemical Industries, Ltd.) with an average particle size of 2.8 microns, 4.5 g of diethylene glycol, and polyethylene 0.5 g of diol (average molecular weight 600) was prepared by dispersing as in Example 1 to prepare a copper oxide dispersion, and calcined on a glass slide to form a dispersion coating film as in Example 1. The surface of the metal copper on the glass slide was often finely cracked. Incomplete copper film ．The SEM observation shows that the paper size of copper powder intergranular paper is in accordance with Chinese National Standard (CNS) A4 specification (210 × 297 mm) -42- 1236931 A7 B7 V. Description of the invention (Insufficient sub-fusion. Industrial use possibility depends on The present invention can use a cheap metal oxide as a raw material to form a metal thin film on a substrate at a relatively low temperature. By controlling the coating thickness of the metal oxide dispersion on the substrate, the film thickness of the metal thin film can be arbitrarily controlled. Also, it can be used. The inkjet coating method directly traces the wiring. This method can omit the light lithography and etching processes required for the conventional wiring formation process, which can save resources and form wiring at low cost. The obtained metal thin film is suitable for the use of metal wiring materials or conductive materials such as electrodes, wiring, and circuits. The obtained porous metal film with a pore size of 1 micron or less and a uniform porous structure is suitable for applications such as catalyst carriers, inorganic filter materials, conductive materials, and thermally conductive materials, as well as applications that require large areas of electrodes. Packing-(Please read the notes on the back before filling out this page) Order Printed by the Consumers' Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs This paper applies the Chinese National Standard (CNS) A4 specification (210X 297 mm) -43-