TW200301154A - Metal oxide dispersion - Google Patents

Abstract

This invention provides a metal oxide dispersion which comprises a dispersion medium and dispersed therein a metal oxide having a particle diameter smaller than 200 nm, and which can form a thin metal film on a substrate through low-temperature heating. When the dispersion is applied to a substrate and then heated, a thin metal film is formed.

Description

20U30ii54 A7 B7 V. Description of the invention (1) Technical field (please read the precautions on the back before filling this page) The present invention relates to a metal oxide dispersion capable of forming a metal thin film, and the use of 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 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 to obtain a metal film. Special devices such as vacuum equipment are not required. The simplified procedure is its advantage, but metal particles Melting usually requires a high temperature above 1000 ° C. Therefore, the substrate is limited to substrates with heat resistance such as ceramics, and is prone to problems such as damage to the substrate due to thermal damage 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. 25 6 1 5 37 discloses a method for forming a metal thin film by 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 the Chinese National Standard (CNS) A4 specification (210X 297 mm) -5- 200301154 A7 B7 V. Description of the invention (2) (Please read the notes on the back before filling out this page) 'It is difficult to mass produce and the cost of metal particles is very high. A method of forming a metal oxide paste in which metal oxide particles are dispersed for forming a metal thin film is also known. Japanese Patent Laid-Open No. 5-9 8 1 95 discloses that a metal oxide paste obtained by dispersing a metal oxide containing a crystalline polymer and having a particle diameter of 300 nm or less is decomposed to obtain a metal thin film. Method. 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 requires a high temperature of 40 (TC to 900 ° C. Therefore, the available substrate must be With heat resistance above this temperature, there is a problem that the available substrate is limited. As mentioned above, the method of coating metal particles or metal oxide dispersions on a substrate and heating to obtain a metal thin film has a low manufacturing cost. However, the use of metal The method of particles has the problem that the particles are extremely expensive. The method of using metal oxide particles must first disperse the particles in the crystalline polymer. The heat treatment required for incineration of the crystalline polymer has a high temperature problem, which is currently not practical. In particular, 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 films are difficult to obtain at lower temperatures for heat treatment. The method for producing a porous metal film is known as a plating method or a slurry method. The plating method is a method in which carbon powder or the like is attached to hair such as polyurethane foam. The surface of the resin skeleton is provided with conductivity, and a metal is plated thereon, and then the foamed resin and carbon powder are incinerated to obtain a porous metal body. However, the method has a complicated process. On the other hand, the slurry method uses metal powder or metal fibers. A method of impregnating and coating on the surface of a foamed resin frame such as polyurethane, and then heating and incinerating the resin component to sinter a metal powder to obtain a porous metal body. This method is impregnated with a porous resin, and the paper size of the raw material is in accordance with Chinese National Standard (CNS) A4 Specifications (210X297 mm) -6- 20030 A7 B7 V. Description of the invention (3) (Please read the precautions on the back before filling this page) The diameter of the powder or metal fiber must be small, usually in the range of tens of microns to hundreds Micron. However, the production of small-sized metal powder requires complicated processes such as spraying and smashing of molten metal, so the raw materials are expensive. Also, because of the large surface area of metal powder, there is a danger of ignition and explosion, so manufacturing equipment The cost is high. Furthermore, the pore diameter of the obtained porous body reflects the pore diameter of the foamed resin impregnated, which is more than tens of micrometers. The oxide powder is mixed with the resin binder, formed into a specific shape with a mold, and then heated in an oxidizing ambient gas. The resin binder is incinerated to obtain a porous metal oxide sintered body, and then calcined in a reducing ambient gas to obtain A method of a porous metal body is also known (Japanese Laid-Open Patent Publication No. 5-195110). However, although this method has the advantage of being able to produce a small-pore metal porous body having a pore size of about 1 micron from cheap metal oxide raw materials, The pressing process has the problem of complicated manufacturing process. In addition, resins such as polyvinyl alcohol resins, butyral resins, and acrylic resins, which are used as resin binders, are intended to completely incinerate these adhesives in a compressed state. High temperature above 1000 ° C, high temperature calcining equipment is required, which is a problem in manufacturing equipment. The Ministry of Economic Affairs, Intellectual Property Bureau, Consumer Cooperatives, printed metal oxide powder and organic binder are mixed without pressure. Forming 'Calcined in a reducing gas, because the organic binder is not in a compressed environment, it can be removed at a lower temperature, such as 700 ° C when using a polyvinyl alcohol binder (Special Table 2 0 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, and only granulated metal powder is obtained, and no porous metal body is 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 a complicated process such as a pressurization process' This paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) ) C (his ^ 3〇ΐί54 A7 ____B7 V. Description of the 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 low-cost, low-temperature heat treatment. A metal oxide dispersion capable of forming a highly adherent thin film on a substrate, and a method for producing a metal thin film on a substrate using the metal oxide dispersion. A method for producing a porous metal thin film is also provided. Disclosure of the invention The inventors have carefully studied 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 having a particle size of less than 200 nm and a dispersion medium, which The dispersion medium contains 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 less than 10. 3 · The metal oxygen of the above item 1 or 2 Polydisperse dispersion, which is printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs of the Sugar Alcohol 4. The metal oxide dispersion of any one of the above items 1 to 3, wherein the polyether compound is based on a carbon number of 2 to 8 Aliphatic polyethers in which the linear and cyclic oxyalkylene groups are repeating units. 5. The metal oxide dispersion of any one of items 1 to 4 above, wherein the molecular weight of the polyether compound is from 150 to 600. 6 · The metal oxide dispersion of the above item 5, wherein the polyether compound is polyethylene glycol and / or polypropylene glycol having a molecular weight of 250 to 1500. 7. The metal oxide dispersion of any one of the above items 1 to 6, wherein The gold paper size is applicable to the Chinese National Standard (CNS) A4 specification (2 丨 〇 < 297 Gong *) -8-C said 2GU30ii54 A7 __ B7 V. Description of the invention (5) It is a metal derived from oxide reduction, The volume resistance is below IX 10.4 ohm centimeters. 8. The metal oxide dispersion of any one of the above items 1 to 7, wherein the metal oxide is copper oxide or silver oxide. 9. The metal oxidation of the above item 8 Dispersion, in which the metal oxide is cuprous oxide. 10. Item 1 to 9 above The metal oxide dispersion according to any one, wherein the content of the metal oxide is 5 to 90% by weight based on the total weight of the metal oxide dispersion. 11. The metal oxide dispersion according to any one of 1 to 10 above. Wherein the metal powder is contained therein and the metal powder and the metal oxide fine particles together account for 5% by weight to 90% by weight of the total weight of the metal oxide dispersion. 12. The metal oxide dispersion of the above item 11, wherein the above The metal powder contains at least one member selected from the group consisting of gold, silver, copper, palladium, platinum, nickel, chromium'aluminum, tin, zinc, osmium, crane, group, lock, money, nail, hungry, f will, urn, noodle, noodle, Iron, wrong metals. 13. The metal oxide dispersion according to any one of the above items 1 to 12, which contains a thermosetting resin, which accounts for 1 to 20% by weight of the total weight of the metal oxide dispersion. 014. Any one of the above items 1 to 13 A metal oxide dispersion containing a reducing agent containing a reducible metal oxide in addition to a polyol and a polyether compound, 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 items 1 to 14 above, wherein the content of the polyhydric alcohol is more than 0.1% by weight of the total weight of the metal oxide dispersion. 95 paper rule ^^ Chinese National Standard (CNS) A4 specification (210X297 Public Envy 1 (Please read the notes on the back before filling this page) C. Order printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs -9- C200301154 A7 B7. V. Description of the invention (6) Weight% or less. Please read the precautions on the back before filling out this page) 16. The metal oxide dispersion of any one of items 1 to 15 above, wherein the content of the polyether compound is 0.1 to 1 of the total weight of the metal oxide dispersion 70% by weight. 17. The metal oxide dispersion according to any one of the above items 1 to 15, wherein the content of the polyether compound accounts for less than the total weight of the metal oxide dispersion by 〇. 丨 wt% 〇18. Calcining the above item 16 Most of the metal oxide dispersions obtained from metal oxide dispersions have a primary particle size of less than 200 nanometers, and the contacting part is fused to form gold. It is a thin film. 1 9 · The above item 17 is obtained by calcining the metal oxide dispersion. Most primary particles are less than 200 nanometers It is a metal thin film with a porous structure formed by agglomeration of fine particles and fusion of contact portions. 2. The method includes a method for manufacturing a metal thin film by applying the metal oxide dispersion of any one of the above items 1 to 16 to a substrate. 2 1. The method of manufacturing a metal thin film according to the above item 20, which includes heat treatment in a non-oxidizing ambient gas. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 22. The method of manufacturing a metal thin film according to the above item 20, wherein Including, after the metal oxide dispersion is coated on the substrate, it is heated and calcined in a passive ambient gas, and then heated and calcined in a reducing ambient gas. 23. Manufacturing of a metal thin film according to any one of the above 20 to 22 Method, wherein the heat treatment temperature is above 50 ° c and below 500 ° c. The best embodiment of the invention Γ ί?, Human-10-20 20301301 54 A7 B7 5. Description of the invention (7) The invention will be described in detail below. The metal oxide dispersion of the present invention contains necessary components such as a metal oxide having a particle size of less than 200 nm, a dispersion medium, and the like. The metal oxide dispersion of the present invention is characterized by ... The bulk 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 size of less than 200 nm, preferably less than 100 nm, and more preferably less than 30 nm. Here, the particle size refers to the primary particle size, which can be measured by morphological observation with an electron microscope, etc. When the particle size is less than 200 nanometers, the metal particles reduced by metal oxides are small, the surface energy becomes large, the melting point decreases, and the metal particles It should be possible to form a metal thin film by low-temperature fusion. The smaller the particle size of the metal oxide, the easier the reduction of the metal oxide particles, so from the viewpoint of the ease of reduction, the smaller the metal oxide particles, the better. When the particle diameter of the metal oxide is 200 nm or more, the fusion between the metal particles obtained by the reduction treatment is insufficient, and a dense and strong structure cannot be used. 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 uranium etching. 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 金属 of a metal obtained by reducing a metal oxide is preferably 1 × 10 ohm cm or less, and more preferably 1 × 0.5 ohm cm or less. The use of such a metal oxide is preferable because the obtained metal thin film has high conductivity. Such metal oxides are, for example, silver oxide, copper oxide, palladium oxide, nickel oxide, lead oxide, cobalt oxide, and the like. Among them, because this paper size applies the Chinese National Standard (CNS) A4 specification (2ωχ297), (please read the precautions on the back before filling this page), τ printed by the Intellectual Property Bureau of the Ministry of Economic Affairs and Consumer Cooperatives 200301154 A7 B7 Ministry of Economic Affairs Printed by the Intellectual Property Bureau's Consumer Cooperatives V. Invention Description (8) Easy reduction and high conductivity after reduction, especially copper oxide and silver oxide. 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, the first silver oxide is preferred. Copper oxides include cuprous oxide and cuprous oxide. The oxidation state of copper is unlimited. It is easy to reduce to copper, and cuprous oxide is particularly preferred. These metal oxides may be commercially available, or they may be synthesized by a known synthesis method. Commercially available products have copper oxide particles with an average particle size of about 30 nanometers (nominal) formed by CI. In addition, for a method for synthesizing cuprous oxide having a particle size of less than 200 nm, a method of heating and synthesizing an acetonylacetone copper complex in a polyalcohol at about 200 ° C (Angewandt Chemie Internation Edtiion, No .40, V.l.2, ρ.359 · 2001), organocopper compounds (copper-N-nitrosophenylhydroxylamine complex) in the presence of a protective agent such as hexadecylamine, in an inert ambient gas , Heating method at a high temperature of about 3 00 ° C (J. Am. Che m. So c., 1999, vol. 12 1, p. 1 1 595) ° Also, the particle size of the metal oxide used in the present invention Below 200 nanometers, it is possible to fuse between the particles only when heat treatment is required. Part of the metal oxide particles can also be replaced with materials other than reducible metal oxides. Materials other than reducible metal oxides include, for example, metals, metal oxides that are not reduced by heating below 500 ° C, or organic compounds, the central part of which is metal, and the surface of which is covered with metal oxides. -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 when screen-printed and coated, they can be dispersed again before printing so that the aggregates do not block the mesh. In addition, for the application of inkjet coating (please read the precautions on the back before filling out this page) This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) -12-

20U30I 5 4 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 5. In the description of invention (9), 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%. If it is less than 5% by weight, the thickness of the metal film obtained by a single coating and calcination is low, and when it exceeds 95% by weight, the dispersion viscosity is too high, and it may be difficult to apply it to a substrate. The dispersion medium used in the present invention is an organic solvent and / or water. Examples of the organic dispersion medium include liquid alcohol solvents, ketone solvents, amidine solvents, ester solvents, and ether 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 Diol, 1,2-propanediol, 1,3-butanediol, pentanediol-2,4, 2-methylpentanediol-2,4, hexanediol-2,5, heptanediol-2 Polyol solvents such as 4,2-ethylhexanediol-1,3, diethylene glycol, dipropylene glycol, hexanediol, octanediol, triethylene glycol, tripropylene glycol, glycerol, and ethylene glycol mono Methyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol monophenyl ether, ethylene glycol mono-2-ethyl ether Butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl this paper scale applicable Chinese National Standard (CNS) A4 size (210X297 mm) (Please read the back of the precautions to fill out this page)

-13- C200301154 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (10) Ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, 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 ethyl 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 acetone, 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. Methylamine-based solvents include formamide, N-methylformamide, N, N-dimethylformamide, N-ethylformamide, N, N-diethylformamide, and acetamide. , N-methylacetamide, N, N-dimethylacetamide, N-ethylacetamide, N, N-diethylacetamide, N-methylpropanamide, N-formamidine Pyrrolidone, N-formamylmorpholine, N-formamylpiperidine, N-formamylpyrrolidine, N-acetamylmorpholine, N-acetamylpiperidine, N-acetamylpyrrolidine Wait. Ester solvents include diethyl carbonate, vinyl carbonate, propylene carbonate, diethyl carbonate, methyl acetate, ethyl acetate, r-butyrolactone, r-valerolactone, n-propyl acetate, and isopropyl acetate 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 mm) ) (Please read the notes on the back before filling this page)

-14- 200301154 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (11) Butyl butyl, methyl amyl acetate, 2-ethyl butyl acetate, 2-ethylhexyl acetate, acetic acid Benzyl methyl ester, cyclohexyl acetate, methyl cyclohexyl acetate, n-nonyl acetate, ethyl acetate, ethyl acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether ester, Diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether ether, diethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, Propylene glycol monobutyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol monoethyl ether acetate, ethylene glycol diacetate, methoxytriethylene glycol esters, ethyl propionate, n-butyl propionate, Isoamyl propionate, diethyl monoate, di-n-butyl oxalate, methyl lactate, ethyl lactate, n-butyl lactate, n-pentyl lactate, diethyl malonate, dimethyl phthalate, phthalate Diethyl acid and so on. 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. These dispersing media may be used alone or as a mixture of two or more dispersing 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 organic solvent and / or water dispersion medium. The other party (please read the notes on the back before filling this page) This paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) -15- ^ C200301154 A7 B7 • V. Description of the invention (12) side, including When the polyol and polyether compound of the metal oxide dispersion are liquids, they have the function of dispersing media. (Please read the precautions on the back before filling out this page} In the present invention, polyol refers to compounds with 2 or more hydroxyl groups. Polyether compounds also refer to compounds with 2 or more ether bonds. Here, it has 2 or more The hydroxyl- and ether-bound compounds are classified as one according to the following criteria; (i) When the number of hydroxyl groups (hereinafter referred to as nl) is greater than the number of ether combinations (hereinafter referred to as n2) (nl > n2), they are classified as polyols (Ii) When nl < n2 or nl = n2, the olefin is a polyether compound. For example, maltotriose is a trisaccharide with 11 hydroxyl groups in the molecular skeleton and 5 ethers combined. It is a polyhydric alcohol. In addition, triethylene glycol is classified as a polyether compound according to the above standards due to the combination of hydroxyl groups and ethers in the molecular skeleton. The metal oxide dispersion printed by the employees' cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs contains polyhydric Alcohol can improve the dispersibility of metal oxide particles. Polyols include, for example, ethylene glycol, diethylene glycol, 1,2-propylene glycol, 1,3-propanediol, 1,2-butanediol, 1,3- Butanediol, 1,4-butanediol, 2-butene-1,4-diol, 2,3-butanediol, pentyl Glycol, 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, etc. In addition, sugar alcohols such as glycerol, threitol, erythritol, pentaerythritol, pentaerythritol, and hexitol may also be used. , Pentaerythritol contains xylitol, ribitol, arabinitol. Also, hexitol includes mannitol, sorbitol, sweet alcohol, etc. Also, glyceraldehyde, dihydroxyacetone, threose, red Mosulose, erythrose, arabinose, ribose, ribulose, xylose, xylulose, lyxose, glucose, fructose, mannose, idose, sorbose, gulose, talose, Tagatose, galactose, allose, atroose, lactose, isomaltose, heptane. Paper size is applicable to Chinese National Standard (CNS) A4 specification (210X297 mm) " -16- c200301154 A7 B7 V. Invention Explanation (13) Sugars such as sugar, heptose, maltobiose, lettuce diose, trehalose, etc. These polyols are reducible and advantageous when metal oxides are reduced. (Please read the notes on the back first (Fill in this page again.) The best polyols are those with less than 10 carbon atoms. Among them, those with liquid viscosity and low viscosity have the effect of dispersing media as described 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, Pentylene glycol, hexanediol, octanediol, etc. Among the polyhydric alcohols, sugar alcohols such as glycerol, threitol, erythritol, pentaerythritol, pentaerythritol, and hexitol are particularly beneficial for the promotion of metal oxide The anticoagulant properties of the metal oxide particles in the dispersion are better. The preferred amount of the polyol is 0.1% to 95% by weight, and 1% to 90% of the total weight of the metal oxide dispersion. % Is more preferable. 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 in combination 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 dispersed uniformly 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. 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 size of the metallic paper is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) -17- c200301154 A7 B7 V. Description of the invention (14) (Please read the precautions on the back before filling this page) Oxide When the content of the polyether compound in the dispersion is 0.1 to 70% by weight or less of the total weight of the metal oxide dispersion, the resulting metal thin film has very few pores and the pore diameter is small, so the density 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 certain, 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 susceptible to reduction by metal oxides, especially those that are prone to low-temperature catalytic decomposition in environmental gases where hydrogen and other gases are present, and those that easily disappear. Polyether compounds are advantageous in reducing metal oxides because of their reducing properties. The viewpoint of dispersibility of polyether compounds printed from metal oxide particles to dispersed media by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs is preferably amorphous polyether compounds, especially repeating units of carbon and 2 to 2 atoms. A linear or cyclic oxyalkylene based 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 ethylene glycol / butanediol binary copolymers, and ethylene glycol / Linear bond terpolymers such as propylene glycol / ethylene glycol, propylene glycol / ethylene glycol / propylene glycol, ethylene glycol / butanediol / ethylene glycol, but are not limited thereto. The block copolymers are binary block copolymers such as polyethylene glycol polypropylene glycol, polyethylene glycol polybutylene glycol, and the like, polyethylene glycol polypropylene glycol, polypropylene glycol polyethylene glycol polypropylene glycol, and the like. ^^ Applicable standards (CNS ΓΑ4 specification (210 X297 mm)-_ 200301154 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs V. Description of the invention (15) Polyethylene glycol Polybutylene glycol Polyethylene glycol Polyether block copolymers, such as linear 3-block block copolymers, etc. The polyether compounds used in the present invention may also contain other functional groups in the molecular structure, such as alcohol groups, ester groups, epoxypropyl groups, Amino group, alkyl group, amido group, amine group, phenyl group, aldehyde group, carbonate group, isocyanate group, sulfonyl group, etc., or a combination of these groups, including alkyl ester group, alkyl amine group and Substituents such as alkyl carbonate groups, but are not limited thereto. It also includes polymerizable vinyl, vinylidene, vinylidene, glycidyl, allyl, and acrylates and methyl groups containing these groups. Acrylate group. These functional groups may have a majority in the molecule, such as sugar, or in the molecule Polyols such as sugar alcohols are also possible. The hydroxyl group contained in the sugar alcohol has a polymer chain structure, which is based on the hydroxyl groups contained in glycerol, threitol, erythritol, pentaerythritol, pentaerythritol, and hexitol. Examples of the polymer chain include glycerol polyethylene glycol polypropylene glycol, erythritol polyethylene glycol polypropylene glycol polyethylene glycol, and the like. Specific examples of the sugar chain include glyceraldehyde, dihydroxyacetone, threose, and erythritol. , Erythrose, arabinose, ribose, ribulose, xylose, xylulose, lyxose 'glucose, fructose, mannose, idulose, sorbose, gulose, talose, tagatose , Galactose, allose, atroose, lactose, isomaltose, glucoheptose, heptose, maltotriose, lettuce triose, trehalose, etc. In addition, the aliphatic polyether used in the present invention, which The terminal group is not particularly limited. The terminal group has a hydroxyl group, a linear, branched or cyclic alkyl ether group having 1 to 8 carbon atoms, an alkyl ester group, an alkylamido group, an alkyl carbonate group, ammonia Modifiers such as ester or trialkylsilyl. Specific examples of modification of terminal groups of aliphatic polyethers are listed below. (Please read first Please fill in this page again if you need to pay attention to this page) This paper size is applicable to China National Standard (CNS) A4 specification (210X297mm) -19- 20030ii54 A7 B7 V. Description of invention (16) (Please read the precautions on the back before filling in this Page) Examples of etherification of at least one terminal alkyl group include etherification with methyl ether, diethyl ether, propyl ether, and propylene oxide ether. Specific examples include polyethylene glycol monomethyl ether, polyethylene glycol dimethyl ether, and polyether. Propylene glycol dimethyl ether, polyisobutylene glycol dimethyl ether, polyethylene glycol diethyl ether, polyethylene glycol monoethyl ether, polyethylene glycol dibutyl ether, polyethylene glycol monobutyl ether, polyethylene glycol dicyclic ring Oxypropyl ether, polyethylene polypropylene glycol dimethyl ether, glycerol polyethylene glycol trimethyl ether, pentaerythritol polyethylene glycol tetramethyl ether, pentaerythritol polyethylene glycol pentamethyl ether, sorbitol polyethylene glycol hexamethyl ether, etc. There are aliphatic polyethers having an ester group at the end, and at least one end is made of, for example, acetate, propionate, acrylate, methacrylate, and benzoate. Ethylene glycols are methylated with terminal carboxyl groups, and those with terminal carboxyl alkyl groups are also suitable. Preferred specific examples are polyethylene glycol monoacetate, polyethylene glycol diacetate, polypropylene glycol monoacetate, polypropylene glycol diacetate, polyethylene glycol dibenzoate, and polyethylene glycol diacrylate. , Polyethylene glycol monomethacrylate, polyethylene glycol dimethacrylate, polyethylene glycol dicarboxymethyl ether dimethyl ester, polypropylene glycol dicarboxymethyl ether dimethyl ester, glycerol polyethylene glycol triacetate Esters, pentaerythritol polyethylene glycol tetraacetate, pentaerythritol polyethylene glycol pentaacetate, sorbitol polyethylene glycol hexaacetate, and the like. Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 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 ammonium groups at the hydroxyl end. The applicable ones include 'polyethylene glycol bis (carboxymethyl ether dimethylamidamine), polypropylene glycol bis (carboxymethyl ether dimethylamidamine), and polyethylene glycol bis (carboxymethyl ether diethylamidamine) ), Glycerol polyethylene glycol tricarboxymethyl ether dimethylamine, pentaerythritol polyethylene glycol tetracarboxymethyl ether dimethylamine, pentaerythritol polyethylene glycol pentacarboxymethyl ether dimethylamine, sorbitol Sugar Alcohol Polyethylene Glycol Hexacarboxymethyl Ether Dimethyl Ammonium Amide This paper is sized to the Chinese National Standard (CNS) A4 (210X297 mm) -20- 200301154 A 7 B7 V. Description of the Invention (17) (Please read first Note on the back, please fill in this page again) Aliphatic polyethers with alkyl carbonate groups at the end, for example, those with at least one end of the above ene glycols added with a methyl ester group, specifically bismethoxycarbonyloxy Polyethylene glycol, diethoxycarbonyloxy polyethylene glycol, diethoxycarbonyloxy Polypropylene glycol, bis three-butoxycarbonyl group, polyethylene glycol, and the like. It is also possible to use aliphatic polyethers modified with urethane group and Sanyuanjishayuan. The modification of trialkylsilyl is preferably modified by trimethylsilyl, which can be modified by trimethylsilylsilane, 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 the hydroxyl group. The low-molecular-weight liquid substance in the polyether compound can itself be used as a dispersion medium. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs as a metal film with high conductivity for the calcination of metal oxide dispersions containing polyether compounds. Polyether compounds are preferably those that can be incinerated after low temperature calcination, and the molecular weight is 150 to 6000 is preferred, and 250 to 15 00 is more preferred. The polyether compound used has an excessively large molecular weight and is not easily incinerated when calcined, and the amount of the polyether compound remaining in the metal film is large. When the amount of the polyether compound remaining in the metal thin film is large, there is a problem that the volume resistance of the metal thin film becomes 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 film-forming property and denseness of the heat-treated metal thin film are low and unfavorable. The amount of the polyether compound added to the metal oxide dispersion is 0.1 to 70% by weight, and more preferably 1 to 50% by weight. When the amount of the polyether compound is less than 0.1% by weight, the paper is reduced from metal oxygen. The paper size is applicable to Chinese National Standard (CNS) A4 (210X297 mm) -21-200301154 A7 B7 V. Description of the invention (18) Metals have low interparticle density and tend to decrease the adhesion to the substrate. On the other hand, when the polyether compound is added in an amount exceeding 70% by weight, the viscosity of the metal oxide dispersion tends to increase, which is not preferable. 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-roller method, the two-roller method, a vertical ball mill, a Berry mixer, a paint shaker, a kneader, a homogenizer, a ball mill, a sand mill, and the like. Dispersion is usually performed by combining a plurality of these 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 dispersing 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 200 nm 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 10 or less carbon atoms is particularly preferred, and the above-mentioned polyether compound is contained in the dispersion medium. It is preferable that the metal oxide dispersion contains metal powder other than the metal oxide particles to improve the characteristics of the metal bonding layer obtained by the heat treatment and reduce the amount of metal oxide particles. There are no particular restrictions on the metal powders that can be used, such as gold, silver, copper, palladium, platinum, nickel, chromium, aluminum, tin, zinc, titanium, tungsten, macro, 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, copper, etc., which are commercially available at low cost, are particularly preferred. Silver due to metal can be applied to this paper. The size of the paper applies the Chinese National Standard (CNS) Α4 specification (210X29 * 7mm) (Please read the precautions on the back before filling this page)

Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs of the 1T-22- C attack 20U30ii54 A7 B7 V. Description of the invention (Thin film is better because of its high oxidation resistance. In addition, if migration resistance is necessary, it can be added to the metal bonding layer Copper powder with strong anti-migration. There is no special restriction on the particle size of these metal powders. It is advisable to use metal powders with better particle sizes according to the purpose. When the metal thin film is obtained by calcination, the particle size of the metal powder is preferably less than 100 microns. 10 microns or less is preferred. When the particle size of the metal powder is above 100 microns, the size difference between the metal powder and the metal oxide particles is too large, and the smoothness of the metal bonding layer is not good. The metal oxide dispersion is used in inkjet inks. The particle size of the metal powder is preferably 200 nanometers or less, and more preferably 100 nanometers or less. The amount of metal powder added to the metal oxide dispersion is based on the total content of the metal powder and metal oxide particles. The total weight of the metal oxide dispersion is preferably from 5% by weight to 95% by weight. The weight ratio of metal powder to metal oxide particles is preferably 9: 1 to 1: 9. The content of metal powder and metal oxide particles is less than 5 weight% When the addition effect is small, if it exceeds 95% by weight, gold will increase the viscosity of the oxide dispersion, which will make coating and filling of the dispersion difficult and unsatisfactory. The weight ratio of the metal powder to the metal oxide particles exceeds 9: 1 to 1. : In the range of 9, the mixing effect of the two particles becomes small and unsatisfactory. It is better to add a thermosetting resin to the above metal oxide dispersion, heat-harden to improve the adhesion to the metal surface, and increase the strength. The thermosetting resin must be soluble in the dispersing medium used, without compromising the dispersibility of the metal oxide dispersion, and there are no special restrictions. There are, for example, epoxy resin, phenol resin, lacquer resin, polyimide resin, polyurethane, melamine Resins, urea resins, etc. Epoxy resins such as bisphenol A epoxy resin, bisphenol F epoxy resin, etc. Paper size is applicable to Chinese National Standard (CNS) A4 specification (210X297 mm) (Please read the note on the back first (Fill in this page again)

T Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs -23-20U30ilb4 A7 B7 V. Description of the invention (20) Grease, (cresol) lacquer type epoxy resin, halogenated bisphenol type resin, m-phenylene difluoride type, four Hydroxyphenol ethane type, polyol polyglycol type, triglyceride type, polyolefin type, epoxidized soybean oil, cyclopentadiene dioxide, ethylene cyclohexene dioxide, and the like. Liquid epoxy resins are preferred due to their low viscosity. Examples include phenoxy-based monoglycidyl ether, bisphenol A diglycidyl ether, propylene glycol diglycidyl ether, propylene glycol diglycidyl acid, and adipic acid Alcohol diglycidyl ether, hydrogenated bis (A) diglycidyl ether, neopentyl glycol diglycidyl ether, glycerol diglycidyl ether, N, N-diglycidyl aniline, N, N -Diglycidyl toluidine, trimethylolpropane triglycidyl ether, glycerin triglycidyl ether and various liquid polysiloxane diglycidyl acids, etc., can be good in liquid epoxy resins. Alcohol-type epoxy resins dispersed in a polyol dispersion medium are preferred, and examples thereof include polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, and 1,4-butanediol diglycidyl ether. The epoxy hardener used in the present invention may 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, Dimethylaminofluorenyl phenol and the like, acid anhydrides include phthalic anhydride, hexahydrophthalic anhydride, and the like, and difluoroboramine complexes include BF 3 -piperidine complex and the like. Also, a bisphenol compound such as bis A may be used. Diamine '2-ethyl-4-methylimidazole, ginsyl (methylamino) silane and the like can also be used. Resin-based hardeners include polysulfide brewed resins made of linolenic acid dimer and ethylene fenuline, etc., and polysulfide brewed resins with sulfo 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 acid anhydride type and other paper sizes apply the Chinese National Standard (CNS) A4 specification (210X297 mm) '-24-(Please read the precautions on the back before filling this page. ) C. Printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, C. 200301154 A7 B7 V. Description of the invention (21) When reacting with stoichiometry and epoxypropyl groups, the optimal addition amount is determined by the epoxy equivalent. The catalyst reaction is generally 3 to 30% by 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 obtained by heating and condensing a precursor polyamidoacid solution, and can be used in the polyamidoacid of the present invention. They can be produced from a tetracarboxylic dianhydride and a diamine-based compound. 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 >, 4 —-biphenyltetracarboxylic dianhydride, 2,3,3 >, 4 —-diphenyl Ketone tetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis [5- (3,4-dicarboxyphenoxy) phenyl] propanedi Anhydride and the like, diamino compounds include, for example, m-phenylenediamine, p-phenylenediamine, 2,4-fluorenediphenyldiamine, 3,3 diaminodiphenyl ether, 3,4'diaminodiphenyl ether, 4 , 4'diaminodiphenyl ether, 3,3 > -diaminodiphenylsulfone, 4,4 / -diaminodiphenylsulfone, 3,4, -diaminodiphenylsulfone, 3,3 > -Diaminodiphenylmethane, 4,4 > -diaminodiphenylmethane, 3,4 > -diaminodiphenylmethane, 4,4 > -diaminodiphenylaso, 3,- Diaminodiphenyl ketone, 4,4 > -diaminodiphenylketone, 3,4 " -diaminodiphenylketone, 2,2 > -bis (4-aminophenyl) propane Wait. 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 applicable. The size of this paper applies to Chinese National Standard (CNS) Α4 size (210X297 mm) (Please read the precautions on the back before filling this page). C ·

Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs of the Ministry of Economic Affairs of the People's Republic of China 1-25T 2GU30if5 4 A7 B7 V. Description of the invention (22) and the addition effect is small at 0.1% by weight, and if it exceeds 20% by weight, the conductivity of the metal bonding layer is significant It is not suitable for metal bucket formation. In the present invention, the polyhydric alcohol and polyether compound have reducing properties, and have the effect of gastrointestinal & metal oxides. In addition to the polyhydric alcohol and polyether compounds, H can be added to metal oxide dispersions to reduce metal The reduction of the oxide is uniform, and it is preferable that the metal oxide is more easily reduced. At this time, it is only necessary to be able to reduce the metal oxide, and there are no particular restrictions on the reducing agent that can be used, either inorganic reducing agent or organic reducing agent. Examples of the inorganic reducing agent include hydrides such as sodium borohydride and lithium borohydride; sulfur compounds such as sulfur dioxide; salts of lower oxides such as sulfite; hydrogen iodide and carbon. Examples of organic reducing agents other than polyols and polyether compounds include aldehydes, hydrazines, diimines, and oxalic acid. Aldehydes include, for example, formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, isobutyraldehyde, valeraldehyde, isovaleraldehyde, trimethylacetaldehyde, hexanal, heptanoic acid, octaldehyde, nonan, undecanal, lauric enzyme, Tridecanoic acid, myristic acid, pentaaldehyde, palmitaldehyde, heptaaldehyde, stearyl aldehyde and other aliphatic saturated aldehydes, glyoxal, succinaldehyde and other aliphatic dialdehydes, acrolein, crotonaldehyde, propargaldehyde, etc. Aliphatic unsaturated aldehydes, benzaldehyde, o-tolualdehyde, m-tolualdehyde, p-tolualdehyde, salicylaldehyde, cinnamaldehyde, α-naphthaldehyde, Θ-naphthaldehyde and other aromatic aldehydes, and heterocyclic aldehydes such as furfural. Diimines are obtained, for example, by thermal decomposition of azodicarboxylate, hydroxylamine-0-sulfonic acid, N-propadienesulfonylhydrazine or N-fluorenylsulfonylhydrazine. Examples of N-propadienesulfonylhydrazine or N-fluorenylsulfonylhydrazine include p-toluenesulfonylhydrazine, benzenesulfonylhydrazine, 2,4,6-p-isopropylbenzenesulfonylhydrazine, chloroethinhydrazine, O-Nitrobenzenesulfonylhydrazine, m-nitrobenzenesulfonylhydrazine, p-nitrobenzenesulfonylhydrazine, etc. This paper size is applicable to Chinese National Standard (CNS) A4 specification (21〇297297). --------, _ installed-(Please read the precautions on the back before filling this page) Order the intellectual property of the Ministry of Economic Affairs Printed by the Bureau ’s Consumer Cooperatives -26- C200301 5 4 A7 B7 V. Description of the Invention (The content of reducing agents other than polyhydric alcohols and polyether compounds' is based on the total weight of the metal oxide dispersion of 0.1 to 70% by weight. 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 of the fired metal film and its adhesion to the substrate It is also possible to add metal oxide precursors, such as metal oxides, to metal oxide dispersions. Metal oxides such as the general formula M (0Rl) n, where M is a metal element. R1 is an alkyl group, and η is an oxidation of a metal element The number M is such as silicon, titanium, hafnium, aluminum, etc. The alkyl group is, for example, methyl, ethyl, isopropyl, n-butyl, tertiary butyl, etc. The representative metal oxides are tetramethoxysilane, tetra Ethoxysilane, tetra (n-propoxy) silane, tetra (isopropoxy) silane, tetra (n-butoxy Silicon compounds such as silane), tetra (secondary butoxy) silane, tetra (tertiary butoxy) silane, titanium tetraethoxy, tetra (n-propoxy) titanium, tetra (isopropoxy) Titanium compounds such as titanium, tetra (n-butoxy) titanium, tetra (secondary butoxy) titanium, and tetra (tertiary butoxy) titanium, etc. These compounds are liquid and easily dispersed in metal oxide dispersions. It is also preferable 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 methyl, ethyl, propyl, phenyl, and butyl. The method for dispersing metal powder, thermosetting resin, reducing agent, metal alkoxide and other materials in the metal oxide dispersion can be ultrasonic method, mixer method, three-roll method, two-roll method, vertical ball mill, bauber General methods such as mixers, paint shakers, kneaders, homogenizers, ball mills, and sand mills. 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 size applies Chinese National Standard (CNS) A4 specification (210X297 mm) (Please read the precautions on the back before filling out this page) Binding and ordering Printed by the Intellectual Property Bureau Staff Consumer Cooperatives of the Ministry of Economics -27- 2003011 ^ 4 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. 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 the metal thin film). The substrate can be an inorganic or organic substrate. The inorganic substrate can be a glass substrate, a semiconductor substrate such as silicon and germanium, a compound semiconductor substrate such as gallium-arsenic, indium-antimony, etc., and a thin film of other substances can be formed on the surface before use. The thin film can be made of aluminum, titanium, chromium, nickel, copper, silver, molybdenum, tungsten, titanium, platinum, gold and other metals, silicon dioxide, fluorinated glass, phosphorous glass, borophosphoric glass, borosilicate glass, polycrystalline silicon , Inorganic compounds such as aluminum oxide, titanium oxide, oxide pins, silicon nitride, titanium nitride, giant nitride, boron nitride, hydrogenated silsesquioxane, ITO (indium tin oxide), Thin films made of sesquioxane, amorphous carbon, fluorinated amorphous carbon, polyimide, etc. Organic substrates are not limited if the heat treatment temperature of the metal oxide dispersion is not damaged by heat, and can be used, for example Polyimide substrates, polyethylene terephthalate (PET) substrates, aromatic polyimide substrates, epoxy substrates, fluororesin substrates, etc. Before forming a metal thin film, you can first improve adhesion, etc. It can be treated by physical methods such as plasma treatment and electron beam treatment, and can also be treated by chemical methods such as adhesion promoters. The adhesion promoters can be so-called silane coupling agents, aluminum chelates, etc. The preferred ones are 3- Aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl Group) -3-aminopropylmethyldimethoxysilane, vinyltrichlorosilane, vinyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-chloropropylmethyldichloro Silane, 3-chloropropylmethyldimethoxysilane, 3-chloropropane (Please read the precautions on the back before filling out this page) _ι · 装 · 1 This paper size applies to China National Standard (CNS) A4 specification (210 × 297 mm) -28-c said 20031 5 4 A7 B7 V. Description of the invention (2 "methyl methyl diethoxysilane, 3-mercaptopropyl trimethoxy Silane, 3-glycidoxypropyltrimethoxy-trioxide, 3-glycidoxypropylmethyldioxolithium, 3-methylpropanyloxypropyldimethoxy Keystone Xiyuan, 3-Methylpropionate oxypropylfluorenyldimethoxysilane, hexamethyldisilammonium, ethyl ethylacetate diisopropoxy aluminum, ginseng (ethyl ethyl acetate (Ester) aluminum, bis (ethyl ethyl acetate) aluminum monoethyl ethyl acetate, ginseng (ethyl ethyl acetate), etc. In the application of these adhesion promoters, other additives can be added if necessary, and the solvent Use diluted. The adhesion promoter can be treated by known methods. In order to improve the adhesion with the organic substrate, a method of immersing the organic substrate in an alkaline aqueous solution and heating can also be adopted. For example, polyimide resin can be treated in a potassium hydroxide solution of about 5M for about 5 minutes, and the imidene ring is cleaved to generate a carboxyl group to give a nail anchor effect. When the metal oxide dispersion of the present invention is used to form a metal thin film on a substrate, the metal oxide dispersion is first coated on the substrate. Application method The general method used for applying the dispersion to a substrate can be used, and examples thereof include a screen printing method, a dip coating method, a spray coating method, a spin coating method, and an inkjet method. When the dispersion is coated on the substrate, the coating thickness is preferably from 0.1 to 100 m, and more preferably from 1 to 30 m. After the dispersion is coated on a substrate, the substrate is heat-treated at a temperature sufficient to reduce the metal oxide to metal to form a metal thin film on the substrate. When the obtained metal film is easily oxidized, it is preferable to perform heat treatment in a non-oxidizing ambient gas. When it is difficult to reduce metal oxides only by reducing agents (polyols, polyether compounds, additional polyols, and reducing agents other than polyether compounds) in metal oxide dispersions, calcination in a reducing ambient gas is preferred. For this paper size, the Chinese National Standard (CNS) Α4 specification (210X297 mm) is applied (Please read the precautions on the back before filling this page)

Printed by 1T Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs -29- C Price 20U30ii54 A7 B7 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (g After calcination in inert ambient gas, followed by reducing environment The metal film obtained by calcination in the gas is better because the density is further improved. Non-oxidizing ambient gas is an ambient gas that does not contain oxidizing gases such as oxygen. There are inert ambient gas and reducing ambient gas. Inert ambient gas Refers to an ambient gas filled with inert gases such as argon, helium, neon, nitrogen, etc. Reducing ambient gas refers to an ambient gas in which reducing gases such as hydrogen and carbon monoxide are present. These gases can be filled in a calciner and sealed. The system calcination can also make the calcining furnace a circulation system •, which circulates these gases. When calcining in non-oxidizing ambient gas, the calcining furnace can be temporarily evacuated to remove oxygen and replaced with non-oxidizing gas. Calcination can be used in Canada. It can be carried out under pressure or in a reduced pressure. In these reduction treatments, the heat treatment temperature is preferably 50 ° C to 500 ° C, and 80 ° C above 40 (more preferably below TC, more preferably above 100 ° C and below 350 ° C. Polyol compounds and / or polyether compounds, essential components of the metal oxide dispersion of the present invention, can be incinerated at such a relatively low temperature ( Or decomposition). Metal oxides can be reduced at temperatures below 50 ° C. The storage stability of metal oxide dispersions tends to deteriorate. Above 500 ° C, the heat resistance of most organic substrates must be exceeded. Can not be used on organic substrates, so they are not good. The time required for heat treatment 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. Oxide of copper, while the coating film is at the micron level, hydrogen is used directly as the reducing gas without dilution, and the heat treatment temperature is set at 20 ° C to 300 ° C in 1 to 2 minutes. The same metal oxide, particle size The smaller one is easier to reduce than the larger one. Therefore, when the particle size is large, it is necessary to burn the satin in reducing ambient gas. When the particle size is small or only blunt. Note for this page, please fill in this page), 11 papers The scale is applicable to the Chinese National Standard (CNS) A4 specification (210X 297 mm) -30-20U30ii54 A7 B7 V. Description of the invention (2) Calcination in the ambient environment gas can be reduced. Calcination in the inert environment gas may form at this time Practically non-problematic metal thin film. The metal thin film obtained by calcining the metal oxide dispersion of the present invention is obtained by using metal oxide particles having a particle size of less than 200 nm as a raw material, and the microstructure is obtained by reducing the metal oxide particles of the raw material. The structure of metal particles with a primary particle size of less than 200 nanometers fused to each other. More specifically, it is a structure of metal particles with a primary particle size of less than 200 nanometers fused to each other to form particles. The particles contact and fuse to form a thin film structure. It was confirmed by microscopic observation of the calcined metal thin film. The size of the metal particles formed by the fusion of metal particles obtained by the reduction of metal oxide particles varies with the ambient gas, temperature, and processing time of the heat treatment. High-temperature, long-term heat treatment will make the metal particles larger. In addition, when heated in a reducing ambient gas, the metal particles tend to become larger. The larger the metal particles, and the smaller and less porous structure between the metal particles and the densely stacked metal particles, the closer the metal film's conductivity is to that of the metal body, so it is more suitable as a conductive film. As described below, depending on the content of the polyether compound in the metal oxide dispersion, the metal thin film structure obtained by calcining the metal oxide dispersion is different. A metal film calcined by a metal oxide dispersion with a polyether compound content of 0.1 to 70% by weight of the total weight of the metal oxide dispersion. The metal particles are densely stacked with each other, and the volume resistance is close to that of the metal body. Therefore, it is suitable for, for example, There are wiring materials and connection materials required for low volume resistance in the construction field. On the other hand, the content of polyether compounds accounts for the total metal oxide dispersion. The paper size applies the Chinese National Standard (CNS) A4 specification (210X 297 mm) (please read the precautions on the back before filling this page).

、 1T Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs-31-200301154 A7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs ___ B7 V. Description of the invention (3 Metal oxide dispersions weighing less than 0.1% by weight The obtained metal film has a porous structure and a large surface area, and is suitable for applications such as electrodes. With the manufacturing method of the present invention, a porous metal film having a pore diameter of 1 micrometer or less can be manufactured. The manufacturing method of the metal film of the present invention is a reduction of metal oxides The method of producing fine metal particles from fine particles and fusing them to obtain a metal thin film does not require pressure because of the spontaneous fusion attraction between the particles generated by the reduction, and as mentioned above, the primary particle size of the metal oxide fine particles is less than 200 nm, which is very It is small, and the polyether compound and the polyol itself are reducing, and the metal particles should be susceptible to spontaneous fusion. The polyol or the polyether compound is calcined at a relatively low temperature, which is not easy to occur in the metal film due to oxidation, decomposition, volatilization, and the like. And other insulation components remain. Therefore, the volume resistance of the metal thin film is low. Also, as described above, the metal oxide content is adjusted. The content of the polyether compound in the dispersion is easy to obtain a porous metal film. Then, by controlling the coating thickness of the metal oxide dispersion on the substrate, the film thickness of the obtained metal film can be arbitrarily controlled, especially for the formation of extremely fine circuits. The thin metal layer has the advantage of being easy to form, and is particularly suitable for use in backing metal foils, etc. When the metal oxide dispersion contains metal powder, the metal particles produced by the reduction of metal oxide particles between the metal powders after calcination are fused. 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. The metal obtained by metal oxide reduction * and the metal of the metal powder may be the same or different. Metals constituting the 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, iron This paper size applies Chinese National Standard (CNS) A4 specification (210X 297mm) '-32- (Please read the precautions on the back before filling this page) 20U30if5 4 A7 B7 V. Description of the invention g. Lead and metal films contain at least one of these metals. (Please read the precautions on the back before filling out this page.) The method for manufacturing the metal film of the present invention is to generate metal particles on the spot at relatively low temperature calcination, so that The method of fusing inter-particles to produce a metal thin film uses raw materials that are not expensive metal particles but inexpensive metal oxides, so it has the advantage of being able to manufacture metal thin films at low cost. In addition, the metal oxide particles do not need to be dispersed in the crystal high The special media such as molecules (which need to be pyrolyzed) can form metal films by heat treatment at a relatively low temperature below 500 ° C, so it has the advantage of low process cost. In other words, the metal films of the present invention. The manufacturing method is a method of manufacturing a metal thin film by using a low-temperature raw material and a low-temperature calcination process. Examples Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs The following examples are used to illustrate the present invention in detail, but the present invention is not limited thereto. The primary particle diameter of the copper oxide particles and the surface morphology of the metal thin film obtained in the present invention are measured by observing the surface with a scanning electron microscope (S_47 00) manufactured by Hitachi. The average secondary particle diameter of the metal oxide in the metal oxide dispersion was measured using a laser scattering particle size cloth (LA-920) manufactured by Horiba. The volume resistivity of the obtained metal thin film was determined using a low-resistance meter (LOWRESTER GP (manufactured by Mitsubishi Chemical Corporation)) by the four-short needle method. (Example 1: Preparation of copper oxide fine particle dispersion and production of porous copper thin film Example) Add 5 grams of copper oxide nano particles (particle size 10 to 100 nanometers, nominal average particle size 30 nanometers, manufactured by CI Chemical Co., Ltd.) to 5 grams of diethylene glycol. This paper is applicable to China. Standard (CNS) A4 specification (210X297 mm) -33- 交 .c200301154 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (3d KEYENS (shares) system stirring defoaming machine (HM-5 00) The dispersion process was performed under the conditions of 10 minutes in the stirring mode and 5 minutes in the defoaming mode to obtain a copper oxide particle dispersion. The obtained copper oxide particle dispersion was coated on a glass slide to become 2 cm in length, 1 cm in width, and 20 μm in thickness. The above glass slide is sent into a calcining furnace, which is degassed by a vacuum pump and then circulated with hydrogen at a flow rate of 1 liter / minute. The temperature of the calcining furnace is increased from room temperature to 250 ° C in 1 hour, and reaches 250 ° C. It is then calcined at this temperature for 1 hour. After cooling Take out the slide glass and observe it. The obtained copper thin film is a porous film with a thickness of 4 micrometers and a pore diameter of about 0.3 micrometers. The film is easily peeled off from the glass slide with an adhesive tape. Example 2: Example of preparing a copper oxide particle dispersion to produce a porous copper film) The dispersion medium was changed to ethylene glycol, and the copper oxide particle dispersion was prepared in the same manner as in Example 1. The calcination temperature was changed to other than 200 ° C. The hydrogen calcination of the copper oxide dispersion was carried out in the same manner as in Example 1. The film was easily peeled from the glass slide with an adhesive tape. The volume resistance of the film was 6 × 10 5 ohm cm. After cooling, the glass slide was taken out for observation. , A porous copper film having a porous structure with a thickness of 4 micrometers and a pore diameter of about 0.2 micrometers is formed. (Example 3: Example of preparing a copper oxide microparticle dispersion to produce a porous copper film) The dispersing medium was changed to diethylene glycol and The 1: 1 mixture of water is prepared by the dispersion method of copper oxide particles in the same manner as in Example 1. Calcination of ambient gas (please read the precautions on the back before filling this page) The paper size applies to Chinese national standards CNS) A4 specification (210X 297 mm) -34- p. C β (200301154 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. Description of the invention (31) The body is changed to argon and the calcination temperature is 3 5 0 ° C, the calcining furnace is a closed system. The temperature of the calcining furnace is increased from room temperature to 350 ° C in 1 hour, and it is heated at this temperature for 1 hour. After cooling, the glass slide is taken out as It was observed that a porous copper film having a thickness of 5 micrometers and a pore diameter of about 0.5 micrometers was obtained. In addition, the film was easily peeled from the glass slide with an adhesive tape, and the volume resistance of the film was 5 × 10-5 ohm cm. (Example 4: Modified copper oxide Microparticle dispersion, example of manufacturing copper thin film) Mixed copper oxide nano particles (particle size 10 to 100 nanometers, nominal average particle size 30 nanometers, CI Chemical Co., Ltd.) 5 g, polyethylene glycol (average With a molecular weight of 600, 1 g of Wako Pure Chemical Industries, Ltd. and 4 g of ethylene glycol) (wako Pure Chemical Industries, Ltd.) 4 g, copper oxide fine particle dispersions were obtained under the same conditions as in Example 1. The obtained copper oxide fine particles were coated on a glass slide to have a length of 5 cm, a width of 1 cm, and a thickness of 10 m. The slide glass was put into a calcining furnace, and the furnace was degassed by a vacuum pump, and then passed through at a flow rate of 1 liter / minute. The calcining furnace was 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 microns was formed on the glass slide. This film has a high adhesion to a glass slide and cannot be peeled off by a tape peel test. The volume resistance of this film is as low as 1.5x 1 (T5 ohm cm.) (Examples 5 to 7: Examples of preparing copper oxide particle dispersions to produce copper films) Mixed copper oxide nano particles (particle size 10 to 100 nanometers) , Nominal average particle size of 30 nanometers, 5 grams of CI Kasei Co., Ltd., 4.5 grams of ethylene glycol (manufactured by Wako Pure Chemical Industries, Ltd.), and polyethylene with average molecular weights of 400, 600, and 1,000 each Diol (and (please read the precautions on the back before filling out this page) This paper size applies to China National Standard (CNS) A4 (210X297 mm) -35- 200301154 A7 Printed by the Employees ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs_ ______B7 V. Description of the invention (3) 0.5 g of Guangpure Pharmaceutical Industry Co., Ltd. The copper oxide particle dispersion was obtained under the same dispersion conditions as in Example 丨. A copper thin film was formed as in the example. The obtained copper thin film and glass carrier The adhesiveness of the sheets is high, and they cannot be peeled off by the peel test. The volume resistance of these films is as low as 2 to 3 x 10 · 5 ohm centimeters. (Example 8: Preparation of copper oxide particle dispersions to produce copper films Example) Mixed copper oxide nano particles (particle size 10 to 10 0 nanometers, nominal average particle size 30 nanometers, 4 grams of CI Kasei Co., Ltd., 2 grams of water, and 2 grams of polyethylene glycol (manufactured by Wako Pure Chemical Industries, Ltd.) with an average molecular weight of 400 grams. A copper oxide fine 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 an adhesive tape, and the volume resistance 値 was 4 x 10-5 ohm cm. (Example 9: Synthetic suboxide Copper particle dispersion, an example of manufacturing a copper film). A glass three-necked flask was charged with 2.7 g of copper acetate (made by Wako Pure Chemical Industries, Ltd.), 0.9 g of purified water, and 90 ml of diethylene glycol. In an oil bath The medium temperature was raised to 1 90 ° C, and the temperature was continuously heated for 2 hours. After 2 hours of reaction, it was cooled to room temperature, and the product was centrifuged by a centrifugal separator made by Hitachi Koki Co., Ltd. The unreacted Copper acetate, etc. Add 100 ml of diethylene glycol to the centrifugal sediment, disperse it with ultrasound, centrifuge it, and settle the cuprous oxide particles with a particle size greater than 1000 nm at a gravity of 20,000 G. Cuprous oxide below 100nm in the upper liquid Separated from the heart, settled by gravity at 35,000G to obtain precipitates of cuprous oxide particles below 1000 nm. Part of the obtained particles were dried on a glass slide at 85 ° C under vacuum, and then used with an electron microscope ^ paper size applicable to China National Standard (CNS) A4 Specification (210X 297 male " " (Please read the precautions on the back before filling this page) -36- c20030 ι5 4 A7 B7 V. Description of the invention ((Please read the precautions on the back before (Fill in this page) Observe the surface morphology. The average particle size of cuprous oxide is 30 nm to 100 nm. The average particle size is 80 nm. The average secondary particle diameter observed by laser scattering method was 120 nm. 0.32 g of cuprous oxide particles were added with polyethylene glycol (average molecular weight 400, manufactured by Wako Pure Chemical Industries, Ltd.) 0.12 g, and diethylene glycol 0.18 g, which were dispersed into a cuprous oxide dispersion by ultrasound. The obtained cuprous oxide dispersion was coated on a glass slide to have a length of 5 cm, a width of 1 cm, and a thickness of 30 m. The above slide was put into a calcining furnace, and the furnace was degassed with a vacuum pump, and then circulated with hydrogen at a flow rate of 0.1 liters / minute. The calcining furnace was heated from room temperature to 300 ° C in 1 hour, and after reaching 300 ° C, it was further heat-treated at this temperature for 1 hour. After cooling, it was confirmed that a uniform copper thin film having a thickness of 8 µm was formed on the glass slide. The obtained copper film had high adhesion to a glass slide, and was not peeled by a tape peeling test. The volume resistivity of the film is as low as 4 × 1 (Tδ ohm centimeters. (Example 10: Synthetic cuprous oxide particle dispersion, example of manufacturing a copper film (example of using a mixed dispersion medium)) Staff of the Intellectual Property Bureau of the Ministry of Economic Affairs Cooperative printed 0.30 g of cuprous oxide particles obtained in Example 9 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 It was dispersed into a cuprous oxide dispersion by ultrasound. It was coated and calcined on a glass slide as in Example 9 to obtain a copper film with a thickness of 9 micrometers and a volume resistivity of 6.0 x 1CT6 ohm cm. The obtained copper film and the glass slide * High adhesion, which cannot be peeled off by tape peeling test. (Example 11 · Example of Synthesizing Cuprous Oxide Microparticle Dispersion to Manufacture Copper Film (This paper size applies Chinese National Standard (CNS) A4 Specification (210 × 297 mm)- 37- 200301154 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. Description of the invention (g as an example of calcination of inert ambient gas and reducing ambient gas). The cuprous oxide obtained in Example 9 was calcined. When the particle dispersion is not directly treated with hydrogen at 30 ° C, the glass slide is first placed on a hot plate, and the entire hot plate is circulated with nitrogen. The hot plate is raised from room temperature to 250 ° C and at 250 ° C. Calcined. 1 hour. After cooling, the pre-calcined slides were moved into a calcining furnace. After the furnace was fully evacuated by a vacuum pump, hydrogen was circulated in the furnace, and it was officially calcined at 300 ° C for 1 hour to obtain a film thickness of 5 microns. Copper film. The volume resistance of the copper film is very low 3x 10-6 ohm cm. The obtained copper film has high adhesion to the glass slide and cannot be peeled off by a tape peel test. (Example 12 2: Synthesis of sugar alcohol Example of making cuprous oxide particle dispersion and producing copper thin film 0.1 g of cuprous oxide particles having a particle size of less than 100 nm obtained in Example 9 plus polyethylene glycol (average molecular weight 400, manufactured by Wako Pure Chemical Industries, Ltd.) 0.1 g ', sorbitol 0.1 g, and ethylene glycol 0.7 g, were dispersed by ultrasound to obtain a cuprous oxide dispersion containing 10% by weight of cuprous oxide. The average secondary of cuprous oxide in the dispersion at the time after dispersion The particle size is 120 nm. After the ultrasonic dispersion, the dispersion was left standing overnight, The average secondary particle diameter of the cuprous oxide is unchanged. The obtained dispersion is screen-printed on a polyimide film with a screen printing plate (made by SONOCOM (strand)) with a line-gap of 30 microns. The printability is good. The above glass slide is sent into the calcining furnace, which is degassed by 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 reaches 25 (TC and then in Heat treatment at this temperature for 1 hour. After cooling, take out the polyimide film and observe the surface with a microscope. It can be confirmed that copper wiring is formed without disconnection. (Please read the precautions on the back before filling this page.) This paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) -38- 2uU30ii54 A7 B7 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (y (Example 13: Synthesis of cuprous oxide particles containing sugar alcohol) Dispersion, example of manufacturing copper film) The sugar alcohol used was other than erythrose, and the cuprous oxide dispersion was prepared as in Example 12. After ultrasonic dispersion, it was allowed to stand overnight. The average secondary particle diameter of the cuprous oxide in the dispersion Unchanged, still 120nm. This dispersion had good printability when screen-printed on a polyimide using a screen printing plate having a line-gap of 30 m as in Example 12. The 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 with a microscope. It was confirmed that copper wiring was formed without disconnection. (Example 14: Example of synthesizing copper oxide fine particle dispersion of synthetic metal powder and manufacturing copper thin film) Copper oxide fine particles (particle size 10 to 100 nm, nominal average particle size 30 nm, CI (strand) 5 g , 4 g of ethylene glycol (manufactured by Wako Pure Chemical Industries, Ltd.), 0.5 g of polyethylene glycol (average molecular weight 600), and 0.5 g of silver particles (average particle size 2.5 μm, manufactured by Sigma Aldrich) are used as if implemented The method of Example 1 was dispersed to obtain a copper oxide microparticle dispersion containing silver particles, which was calcined as in Example 1. The obtained copper film containing silver particles has a volume resistance 値 of 7 × l (T5 ohm cm). The obtained film has higher oxidation resistance than a copper film without a copper film without a silver pillar. In addition, the obtained film has a higher adhesion to a glass slide. ， Take off with tape to verify that it does not peel off. (Example 15: Synthetic copper oxide particle dispersion containing epoxy resin, manufacturing. Copper film example) (Please read the precautions on the back before filling in this page)

This paper size applies to China National Standard (CNS) A4 specification (210X 297 mm) -39- 20U30ilb A7 B7 V. Description of the invention (y (Please read the precautions on the back before filling this page) Copper oxide particles (particle size 10 Up to 100 nanometers, nominal average particle size of 30 nanometers, rice, 5 grams of CI (stock), 4.5 grams of ethylene glycol (made by Wako Pure Chemical Industries, Ltd.), 1,4-butanediol diepoxy 0.5 g of lactone and 0.4 g of polyethylene glycol (molecular weight 600) were dispersed as in Example 1. After the dispersion, an epoxy hardener micro-curing hardener (NOVACURE HX-3088, manufactured by Asahi Kasei EPOXY Co., Ltd.) was added. 〇3 grams, 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 that without epoxy resin. Dispersion (Example 16: Example of synthesizing a dispersion of copper oxide particles containing polyimide resin and manufacturing a copper film) Printed bis (4-aminophenyl) ether 1 by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 0.0 g and pyromellitic anhydride 丨 0.9 g dissolved in N-methylpyrrolidone (NMP) 100 g, at room temperature Mix for 1 hour to obtain a polyamic acid NMP solution. Add 2 grams of copper oxide particles (particle size 10 to 100 nanometers, nominal average particle diameter 30 nanometers) to the polyphosphonic acid solution. ) 5 g, and 3 g of ethylene glycol (made by Wako Pure Chemical Industries, Ltd.) were dispersed as in Example 1. The dispersion was coated on a polyimide film (T0RAY · DuPont) cut into 3 cm x 3 cm KAPTON film made by the company (50 micron 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 The resistivity is 9x .1 (T5 ohm cm. The adhesion of the obtained copper film is much higher than that of a film calcined on a polyimide film without polyamic acid. (Example 17: Synthesis of oxidation with a reducing agent) Dispersion of copper particles, made porous This paper is sized according to Chinese National Standard (CNS) A4 (210X297 mm) -40- 2GU30ii54 A7 B7 Printed by Intellectual Property of the Ministry of Economic Affairs ^ Printed by the Consumer Cooperatives (3) Sexual copper film Example) Copper oxide nano particles (particle size 10 to 100 nm, nominal average particle size 30 nm , 5 g of CI Kasei Co., Ltd., 4.5 g of diethylene glycol (Wako Pure Chemical Industries, Ltd.), and 0.5 g of propionaldehyde (Wako Pure Chemical Industries, Ltd.), as in Example 1 The copper oxide fine particle dispersion was dispersed. The obtained dispersion was coated on a glass slide as in the example, and an argon gas was flowed at a flow rate of 0.1 liters / minute from room temperature to 350 ° C in 1 hour at 350 ° C, reaching 350. After ° C, heat treatment is performed at this temperature for 1 hour. The volume resistance of the obtained copper film is as low as 3x 10-5 ohm cm. (Example 8: Example of manufacturing a copper thin film on a silicon wafer) Copper oxide nanoparticles (particle size 10 to 100 nm, nominal average particle size 30 nm, CI Chemical Co., Ltd.) 5 g, ethylene oxide 4.5 g of alcohol (made by Wako Pure Chemical Industries, Ltd.) and 0.5 g of polyethylene glycol (made by Wako Pure Chemical Industries, Ltd.) were dispersed as in Example 1 to obtain a copper oxide fine particle dispersion. 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. The silicon wafer was pre-spun at 1000 ppm for 10 seconds and then spin-coated at 300 rpm for 30 seconds. After the application, the spheroidal crystal circle was calcined as in Example 1. The thickness of the copper film on the silicon wafer is 0.6 micron, and the volume resistance is as low as 6x 10-6 ohm cm. (Example 19: Example of preparing a cuprous oxide dispersion to produce a copper thin film) 60 ml of pure water was added with 8 g of anhydrous copper acetate (manufactured by Wako Pure Chemical Industries, Ltd.), and hydrazine monohydrate was added under stirring at 25 ° C. (Wako Pure Chemical Industries, Ltd.) for reduction (please read the precautions on the back before filling out this page) This paper size is applicable to China National Standard (CNS) A4 (210X297 mm) -41-200301154 A7 B7 5 2. Description of the invention (y (please read the precautions on the reverse side and then fill out this page) reaction to obtain cuprous oxide particles with a particle size of 10 to 30 nanometers. Add 0.5 g of the cuprous oxide particles to diethylene glycol 0.1 G and polyethylene glycol (average molecular weight 200, manufactured by Wako Pure Chemical Industries, Ltd.) 0.4 g. Ultrasonic dispersion was used to modulate a cuprous oxide dispersion. The dispersion was coated on a glass slide to form a length of 5 The width is 1 cm and the thickness is 20 microns. The above slides are sent to the calcination furnace, and the furnace is degassed with a vacuum pump, and then replaced with argon gas. The calcining furnace is heated from room temperature to 350 ° C in 1 hour to reach After 350 ° C, heat treatment at this temperature for 1 hour. After cooling, it will have a thickness of 7 microns and a volume Copper film with resistivity of 4.0x 1CT6 ohm cm. The obtained film has high adhesion to the glass slide and cannot be peeled off by tape peeling test. (Comparative Example 1: Particle size of metal oxide particles) Oxidation with an average particle size of 2.8 microns Copper powder (made by Wako Pure Chemical Industries, Ltd.) 5 g and 5 g of diethylene glycol were dispersed and treated as in Example 1 to obtain a copper oxide dispersion, and calcined as a dispersion film on a glass slide as in Example 1. The surface of the metal copper on the glass slide has many fine cracks, which are incomplete copper films. The particle fusion between the copper powders is insufficient by SEM observation. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs (Comparative Example 2: Metal Oxide Particles) Particle size) 5 g of copper oxide powder (manufactured by Wako Pure Chemical Industries, Ltd.) with an average particle size of 2.8 μm, 4.5 g of diethylene glycol, and 0.5 g of polyethylene glycol (average molecular weight 600) were dispersed as in Example 1. The copper oxide dispersion was prepared as 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 mostly cracked and was an incomplete copper film. The intergranular nature of the copper powder was observed by SEM observation. Paper size Use Chinese National Standard (CNS) A4 specification (210X297mm) -42- 2〇U3〇rf54 A7 B7 V. Description of the invention (Insufficient sub-fusion. Industrial use possibility According to the invention, cheap metal oxides can be used as raw materials. The metal film is formed on the substrate at a relatively low temperature. The thickness of the metal thin film can be controlled arbitrarily by controlling the coating thickness of the metal oxide dispersion on the substrate. In addition, the wiring can be formed by direct drawing using an inkjet coating method. The light lithography and etching processes required for the conventional wiring formation process can be omitted, 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 thin film having a pore size of 1 micrometer 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 area electrodes. (Please read the notes on the back before filling this page)

, 1T

Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs This paper is sized to the Chinese National Standard (CNS) A4 (210 × 297 mm) -43-

Claims (1)

η ^ ^ υϋ3〇χΐ54 Α8 Β8 C8 ^ D8 Force, patent application scope 1 (Please read the precautions on the back before filling this page) 1. A metal oxide dispersion containing a metal oxide with a particle size of less than 200 nm And a dispersion medium, characterized in that the dispersion medium contains a polyol and / or a polyether compound. 2. For example, the metal oxide dispersion in item 1 of the patent application scope, wherein the number of carbon atoms of the polyol is less than 10. 3. The metal oxide dispersion according to item 1 or 2 of the patent application scope, wherein the polyhydric alcohol is a sugar alcohol. 4. The metal oxide dispersion according to any one of claims 1 to 3, wherein the polyether compound is an aliphatic having a linear or cyclic oxyalkylene group having 2 to 8 carbon atoms as a repeating unit. Polyether. 5. The metal oxide dispersion according to any one of claims 1 to 4, wherein the molecular weight of the polyether compound is from 15 to 6000. 6. The metal oxide dispersion according to item 5 of the patent application scope, wherein the polyether compound is a polyethylene glycol and / or polypropylene glycol having a molecular weight of 2 500 or more and 1 500 or less. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 7. If the metal oxide dispersion of any of the items 1 to 6 of the patent application scope, the metal oxide reduced metal has a volume resistance of 1X 1 (Τ4 Ohm centimeter or less. 8 · Metal oxide dispersion according to any one of claims 1 to 7, wherein the metal oxide is a copper oxide or silver oxide. 9 · As the metal of claim 8 An oxide dispersion, wherein the metal oxide is cuprous oxide. 10. The metal oxide dispersion according to any one of claims 1 to 9, wherein the metal oxide content accounts for 5% of the total weight of the metal oxide dispersion. This paper size applies to China National Standard (CNS) A4 specification (210X297 mm) -44- 20U30ii54 A8 B8 C8 D8 Printed by the Consumers' Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs 6. Application for patents ranging from 2 to 90% by weight. 1 1. Such as The metal oxide dispersion according to any one of the claims 1 to 10 of the patent application scope, which contains metal powder, the metal powder and metal oxide fine particles together, accounting for the total weight of the metal oxide dispersion 5 wt% or more and 95 wt% or less 0 2 The metal oxide dispersion according to item 11 of the scope of the patent application, wherein the above metal powder contains at least one * selected from the group consisting of gold, silver, copper, gold, silver, copper, silver, copper , Aluminum, Tin, Zinc, Titanium, Tungsten, Giant, Barium, Rhodium, Ruthenium, Hungry, Bismuth, Iridium, Cobalt, Indium, Iron and Lead The metal oxide dispersion according to any one, wherein the thermosetting resin contains 0.1 to 20% by weight of the total metal oxide 1 dispersion. 14. The metal oxidation according to any one of claims 1 to 13 A dispersion containing a reducing agent capable of reducing a metal oxide other than a polyol and a polyether compound, which accounts for the total weight of the metal oxide dispersion from 0.1 to 70% by weight. The metal oxide dispersion according to any one of items 1 to 14, wherein the polyol content accounts for the total weight of the metal oxide dispersion of 0.1% by weight to 95% by weight. The metal oxide dispersion of any one of 15 items, wherein the polyether compound contains 0.1 to 70% by weight of the total weight of the metal oxide dispersion. 17. The metal oxide dispersion according to any one of claims 1 to 15 of the scope of the patent application, wherein the content of the polyether compound accounts for the metal oxide dispersion Total weight This paper size applies to Chinese National Standard (CNS) A4 specifications (210X297) (Please read the precautions on the back before filling out this page) One Pack · Order-45- Cfen200301154 A8 B8 C8 D8 Intellectual Property of the Ministry of Economic Affairs Printed by the Bureau's Consumer Cooperatives 6. The scope of patent application 3 is less than 0.1% by weight. 1 8. A metal thin film characterized by calcining the metal oxide dispersion as described in item 16 of the patent application, and forming a plurality of metal particles with a primary particle size of less than 200 nm, and forming the contact parts by fusion . 19. A metal thin film having a porous structure, characterized in that: a plurality of metal particles having a primary particle size of less than 200 nm are obtained by calcining the metal oxide dispersion of item 17 in the scope of the patent application, and the contact portions are fused Formed. 20. A method for manufacturing a metal thin film, characterized in that: a metal oxide dispersion according to any one of claims 1 to 16 of an application for a patent is applied to a substrate and then heat-treated. 21. For the manufacturing method of the metal thin film according to the scope of the patent application, the heat treatment in ## is performed in a non-oxidizing ambient gas. 22. For the method for manufacturing a metal thin film according to item 20 of the application, after the metal oxide dispersion is coated on the substrate, it is calcined in a passive ambient gas, and then heated and calcined in a reducing ambient gas. 23. The manufacturing method of the metal thin film according to any one of claims 20 to 22, wherein the heat treatment temperature is 5 (TC above 500 ° C.) This paper size is applicable to Chinese National Standard (CNS) A4 specification (210X297) (Mm) (Please read the precautions on the back before filling out this page) -Installation_ -46- (: 2GU30ii54 (1), the representative representative of this case is: None (2), the component representative symbols of this representative illustration are simply explained :no