KR20000069225A - Metal composition comprising metal acetylide compound, material with metal coat of the same, and its metal coat forming method - Google Patents

Abstract

A metal acetylide compound represented by the general formula M (-C≡C-R) _n (wherein M is a metal atom, n is a valence of a metal atom M, and R is a hydrocarbon group with or without an oxygen atom) Is used as an organometallic source, and resins and organic solvents are blended and kneaded therein to prepare metal compositions such as metal liquids and metal pastes. When the metal composition is applied to a decorative pattern such as porcelain, glass, or electronic component in a desired pattern, and at least the required portion is dried and heated, organic substances other than the metal are decomposed and released, and only the metal is deposited on the pattern. Sinter. This pattern represents decorative metallic luster on decorative articles or forms electrodes on electronic components. Since the metal acetylide compound does not contain sulfur or a halogen element, the metal acetylide compound does not emit environmental pollutants such as sulfurous acid gas or halogen gas even when calcined, thereby contributing to clean environment. Moreover, since it is high in solubility in an organic solvent, it is suitable as a raw material of a metal composition. In addition, since the metal film formed after firing has high smoothness, denseness, metallic glossiness, and electrical conductivity, it is possible to form a decorative article, an electrode of an electronic component, or the like with high quality.

Description

A metal composition containing a metal acetylide compound, a material on which a metal film is formed, and a method of forming a metal film thereof, and a method for forming the metal film thereon {METAL COMPOSITION COMPRISING METAL ACETYLIDE COMPOUND,

In general, in the case of forming an electrode on an insulating substrate, an electronic component, or the like, a metal powder or an organic metal complex is mixed and kneaded with a resin, an organic solvent, or the like to prepare an organic metal paste, and the organic metal paste is insulated by screen printing or the like. There is known a method of coating on an electronic component to form a predetermined circuit pattern, heating the pattern portion to decompose and evaporate an organic component, and depositing a metal into a film. In addition, when forming a decoratively coated metal film on the surface of pottery or the like, a metal liquid having a low viscosity is required, and an organic metal complex soluble in an organic solvent is selected, dissolved and dispersed in the organic solvent to prepare an organic metal liquid. Doing. As such, organometallic complexes are currently used in a wide range of fields such as electronic devices, ceramics, and crafts.

Conventionally, organometallic complexes that can be used for such applications include balsam-based compounds such as terpineol sulfide (C ₁₀ H ₁₈ SAuCl _x ), sulfide terpineol platinum (C ₁₀ H ₁₈ SPtCl _x ) and sulfide terpine Ol palladium (C ₁₀ H ₁₈ SPdCl _x ) and the like are known. These compounds are generally abbreviated as gold balsam, platinum balsam, palladium balsam, and other precious metal balms such as rhodium balsam and ruthenium balsam are known.

The use of such conventional balsamic compounds as a raw material of metal compositions such as metal pastes and metal liquids has left the following problems.

First, in the case of depositing a metal using these metal compositions, the first step cannot be avoided in the process of firing. Since the balsamic compound contains chlorine or sulfur, SO _x or Cl ₂ are inevitably generated as by-products during the firing process. The release of these hazardous substances into the environment not only harms the employee's hygiene environment, but also adversely affects the natural environment in general. Moreover, recovering these harmful substances requires considerable facilities such as a desulfurization apparatus, and even if recovered, it is difficult to recover 100%. Since SO _x and halogen cause damage to the equipment for sintering, a safer metal composition for forming a metal film has been required.

The second is the case where SO _x or the halogen generated during firing damaging evil younghang the material. The material is heated to decompose and evaporate components other than metals, but SO _x or halogen may corrode the material, or sulfur or halogen atoms may diffuse as impurities in the material. In particular, when the material is an electronic component, it sometimes adversely affects its electronic characteristics.

Third, when preparing an organometallic liquid from a balsamic compound, there was a limit to the organic solvent that can be used. For example, the solubility is high in an aromatic solvent, but hardly soluble in an alcohol solvent. There is also a similar limitation on the resin needed to prepare the organometallic paste. For example, when resin is nitrocellulose, it is soluble in solvents, such as butyl carbitol and butyl carbitol acetate, but it does not melt | dissolve in terpineol. Therefore, if the solvent is limited in terms of the organometallic complex, the number of metal pastes that can be produced is limited because the resin can be naturally used, and the use thereof is also limited.

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a metal composition in which metal films such as electrodes and decorative films are formed on the surface of a material, and an application method thereof. The present invention relates to a metal composition capable of keeping the environment clean without generating harmful gases such as SO _x and Cl ₂ , and an application method thereof.

The present invention has been made to improve the above-mentioned drawbacks, and proposes to use a metal acetylide compound containing no sulfur or chlorine as an organometallic complex which is a main component of a metal composition. This metal acetylide compound is represented by the general formula M (-C≡C-R) _n (wherein M is a metal atom, n is a valence of a metal atom M, and R is a hydrocarbon group containing or without an oxygen atom). It does not contain sulfur and a halogen as a member element.

The metal acetylide compound is dissolved and dispersed in an organic solvent to provide a metal composition in the form of an organic metal liquid. The metal acetylide compound, a resin imparting viscosity and an organic solvent are kneaded to provide a metal composition made into an organic metal paste. The metal composition which mix | blended the additive which raises the adhesiveness of a metal film is provided. The present invention also provides a metal composition containing a plurality of metal acetylide compounds having different metal elements.

A metal film forming method is formed by coating these metal compositions in a desired pattern on a surface of a material to form a metal composition film, heating the metal composition film to decompose and evaporate materials other than metal, and sintering the metal to form a dense metal film. do. By this method, a material having a metal film having a desired pattern formed on its surface is provided.

MEANS TO SOLVE THE PROBLEM The present inventors earnestly researched the organometallic complex which does not contain sulfur and a halogen which are a cause of environmental pollution, and is soluble in many organic solvents, and found that the metal acetylide compound which is a kind of acetylene derivative is suitable for the objective of this invention. Based on this fact, the present invention has been completed.

That is, the organometallic complex used in the present invention is a metal acetylide compound represented by the general formula M (-C≡C-R) _n . In this general formula, M represents a metal atom and is composed of a wide range of metal atoms such as Bi, Cu, In, Ni, Ru, Rh, Pd, Ag, Os, Ir, Pt, Au, and the like. Precious metals with high stability are frequently used as metal compositions such as organometallic liquids and organometallic pastes, and the precious metals refer to metal elements of Au, Ag, and platinum groups (Ru, Rh, Pd, Os, Ir, Pt).

n represents the valence of the metal atom M, for example, Au is monovalent and trivalent, Ag is monovalent and divalent, Pt is divalent, tetravalent and hexavalent. That is, not only the value differs depending on the type of metal element, but also a specific metal element has a plurality of valences.

R in the ligand-C≡C-R of the metal acetylide compound is a hydrocarbon group containing or not containing an oxygen atom, and its member elements are C and H, or C and H and O. As for carbon number of hydrocarbon group R, 1-8 are preferable, and, as for carbon number of the whole ligand, 3-10 are preferable. The reason for this is that when the carbon number is low, the metal acetylide compound becomes difficult to dissolve in the solvent and at the same time, the explosiveness increases, which makes handling dangerous. In addition, when the carbon number of the ligand is large, the metal weight in the material is relatively low, and when the organic metal liquid or the organic metal paste is made, the metal film cannot be formed. That is, when using the metal acetylide compound of this invention for a metal composition, even if it is soluble in a solvent, the fixed metal weight is needed. That is, when the number of carbon atoms of the ligand -C≡C-R is in the range of 3 to 10, the metal acetylide compound is easy to dissolve in a solvent and the metal weight is relatively large, so that the metal acetylide compound can be sufficiently used as a metal composition.

Hydrocarbon group R is an aliphatic hydrocarbon group to contain as a hydroxyl group, when oxygen is contained. In this case, it may be linear or it may have a side chain. As an embodiment of the ligand -C≡C-R, propine, 2-propyn-1-ol, 1-butyn-3-ol, 3-methyl-1-butyn- in the form H-C≡C-R 3-ol, 3,3-dimethyl-1-butyne, 1-pentin, 1-pentin-3-ol, 4-pentin-1-ol, 4-pentin-2-ol, 4-methyl-1-pentin, 3-methyl-1-pentin-3-ol, 3,4-dimethyl-1-pentin-3-ol, 1-hexyn, 1-hexyn-3-ol, 5-hexyn-1-ol, 5-methyl- 1-hexine, 5-methyl-1-hexyn-3-ol, 3,5-dimethyl-1-hexyn-3-ol, 1-heptin, 1-heptin-3-ol, 5-heptin-3-ol, 3,6-dimethyl-1-heptin-3-ol, 1-octin, 1-octin-3-ol and the like.

Moreover, when carbon is contained as a hydrocarbon group R, there exists a hydrocarbon group which contains at least the cyclic hydrocarbon contained as a hydroxyl group. This hydrocarbon group may have a cyclic hydrocarbon group in a straight chain or may contain a cyclic hydrocarbon group in a side chain. Of course, the case where all of R is a cyclic hydrocarbon is included. Specific examples of the ligand -C≡C-R are 1-ethynyl-1-cyclopropanol, 1-ethynyl-1-cyclobutanol, 1-ethynyl-1-cyclopentane in the form of H-C≡C-R. Ol, 1-ethynyl-1-cyclohexanol, 1-propyne-3-cyclopropanol, 1-propyne-3-cyclobutanol, 1-propyne-3-cyclopentanol, 1-butyn-4- Cyclopropanol, 1-butyn-4-cyclobutanol, 1-pentin-5-cyclopropanol and the like.

As described above, the metal acetylide compound is composed of only metal elements, carbon, hydrogen, and / or oxygen, and even when decomposed by calcination, carbon dioxide, water vapor, and some hydrocarbons are generated depending on the calcination temperature. merely be, hazardous material with respect to the SO _x and a halogen gas such environment is not created. Therefore, it is an organometallic complex which is very safe and clean with respect to an environment and a living thing.

The metal composition of the present invention is classified into an organometallic liquid and an organometallic paste. An organometallic liquid is a normal liquid because it dissolves and disperse | distributes the metal acetylide compound which is an organometallic complex in an organic solvent. The organometallic paste is obtained by incorporating a metal acetylide compound and a resin for viscosity adjustment into an organic solvent, thereby increasing or decreasing the viscosity depending on the type of use. The liquid metal composition having a low viscosity may be referred to as an organometallic liquid or may be referred to as an organometallic paste, and the boundary between them cannot be clearly defined.

Unlike conventional balsamic compounds, metal acetylide compounds dissolve in a wide range of organic solvents regardless of polarity or nonpolarity. Specific examples of the organic solvent include petroleum solvents, terpineol, butyl carbitol, esters such as ethyl lactate, cellosolves, alcohols, aromatics, DEP (diethyl phthalate), and the like.

The viscosity of the organometallic paste varies depending on the arrival conditions (printing conditions) of the raw material, the firing conditions, and the surface state after firing, and resin is mixed in order to adjust the viscosity. As resin, what is easy to melt | dissolve and disperse in an organic solvent with a metal acetylide compound is calculated | required. Since metal acetylide compounds are dissolved by many organic solvents, the selection range of resins that can be dissolved and dispersed in these organic solvents becomes very wide compared with conventional balsamic compounds. For example, ethyl cellulose, nitrocellulose, aspart, butyral, acrylcopibalsam, dharma and the like or related materials thereof may be used as the resin.

An organometallic liquid is prepared by mixing the metal acetylide compound and the organic solvent described above. In this case, 60 weight part-10 weight part of a metal acetylide compound, and 30 weight part-90 weight part of an organic solvent are preferable, and it is preferable to mix | blend 10 weight part-1 weight part of the additive mentioned later. In addition, a small amount of resin may be added. When the amount of the metal acetylide compound is smaller than this, the metal weight is reduced so that a metal film cannot be formed. If the amount of the metal acetylide compound is larger than this, the metal acetylide compound cannot be dispersed in the organic solvent and precipitates. Therefore, this range can provide a preferable organometallic liquid. It can be set to an optimum compounding quantity corresponding to the conditions, such as the raw material which forms a metal film, heating temperature, film thickness, etc.

In addition, a metal acetylide compound, an organic solvent, and a resin are mixed to prepare an organometallic paste. In this case, as for the compounding quantity of a component, 60 weight part-10 weight part of metal acetylide compounds, 30 weight part-85 weight part of an organic solvent, and 3 weight part-30 weight part of resin are preferable. It is also possible to mix | blend 1 weight part-10 weight part of additives with these if necessary.

The viscosity of the organometallic paste produced in this range is in the range of 50p (poise) to 5000p (poise). When the viscosity is lower than the lower limit, the organometallic paste is close to the organometallic liquid. When the viscosity is higher than the upper limit, it becomes difficult to thin the film thickness when the metal composition arrives on the material surface. The viscosity of the organometallic paste can be freely changed corresponding to its use.

In order to prepare an organometallic liquid or organometallic paste, necessary components are selected from metal acetylide compounds, organic solvents, resins, and additives, and their required weights are filled into a container and uniformly dissolved and dispersed using a kneading apparatus. This mixed solution is passed through one or more layers of mesh to remove debris and large particles. As a result, it is possible to obtain an organometallic liquid and an organometallic paste which are finely and uniformly dissolved and dispersed. Since metal acetylide compounds are considerably more soluble in organic solvents than conventional organometallic complexes, the metal acetylide compounds have the advantage of obtaining a metal composition uniformly dissolved and dispersed by the above simple kneading and stirring process.

The metal composition film is formed on the surface of the material using the organometallic liquid or organometallic paste prepared by the above method. There are many articles in the material, and a very wide range of articles are not limited to a specific article to be the object of the present invention. Examples include ornaments such as ceramics, tiles, and glass products, and electronic components such as electrodes for thermal heads of prints.

Forming a metal composition film having a predetermined pattern on the surface of the material with the organometallic liquid includes simple writing and a dip method. In the case of a metal paste, there are methods such as screen printing, pad printing, transfer, and dip methods.

Next, the metal composition film is fired to form a metal film. The entire material may be introduced into a heating furnace and heated to a firing temperature, or the metal composition film portion on the surface of the material may be locally heated with a gas burner or the like. Upon firing, ligands other than metals in organic solvents, resins, additives, or metal acetylides are thermally decomposed and evaporated, and the remaining metal atoms are bonded to each other and grow to form metal films. This metal film functions as a decorative film in an ornament or an electrode in an electronic component, and functions appropriately depending on the purpose.

The metal composition of this invention has the following characteristics. Since the first does not contain sulfur or chlorine, it does not emit harmful substances such as SO _x or halogen in the firing step, and is clean for the environment, and a device such as a desulfurization device is not needed.

Second, the decomposition temperature of the metal acetylide compound is about 400 ° C., which is slightly lower than that of the conventional organometallic complex. That is, since baking is possible at comparatively low temperature which is 400 degreeC or more, it can apply to many raw materials, such as glass of low melting | fusing point, and can prevent deterioration and thermal deformation of a raw material.

Thirdly, since the metal film after firing is smoothly finished like a mirror surface, it can be used in a field requiring high precision such as an ornament and an electronic component.

Best Mode for Carrying Out the Invention

Best Mode for Carrying Out the Invention The present invention will be described below by way of examples.

Example 1 [Preparation of Gold Paste]

40 parts of gold acetylide, 0.8 parts of bismuth naphthenic acid, 0.08 parts of rhodium acetylide, 6 parts of ethyl cellulose, and 38 parts of terpineol were kneaded into a paste. The finished paste was passed through a mesh to remove debris. After the gold paste arrived on the ceramics and glass by screen printing and fired, a shiny gold pattern was obtained.

Example 2 [Preparation of Gold Paste]

40 parts of gold acetylide, 5.5 parts of bismuth naphthenate, 0.08 parts of rhodium acetylide, 5 parts of nitrocellulose and 39 parts of butyl carbitol were kneaded into paste. This paste was passed through a mesh to remove debris. After the gold paste arrived on the porcelain and glass by screen printing and fired, a shiny gold pattern was obtained.

Example 3 Preparation of Gold and Silver Paste

40 parts of gold acetylide, 5.5 parts of octyl acid bismuth, 10 parts of silver acetylide, 0.1 part of rhodium acetylide, 4 parts of ethyl cellulose, 15 parts of ethyl lactate, and 20 parts of butyl carbitol were kneaded into paste. This paste was passed through a mesh to remove debris. The gold and silver paste arrived on the pottery and glass by screen printing and then fired to obtain a pattern with strong gold luster.

Example 4 [Preparation of Gold Paste]

14 parts of gold acetylide, 2.0 parts of octyl acid bismuth, 0.7 parts of silver acetylide, 0.028 parts of rhodium acetylide, 6 parts of ethyl cellulose, 4 parts of nitrocellulose, 30 parts of ethyl lactate, and 40 parts of butyl carbitol were kneaded to form a paste. . The finished paste was passed through a mesh to remove debris. When this gold paste arrived on the pottery and glass by screen printing and baked, the shiny gold pattern was obtained.

Example 5 Preparation of Platinum Platinum Paste

12 parts of platinum acetylide, 19 parts of gold acetylide, 3.3 parts of octyl acid bismuth, 0.048 parts of rhodium acetylide, 8 parts of ethyl cellulose, 20 parts of ethyl lactate, and 35 parts of butyl carbitol were kneaded into paste. The finished paste was passed through a mesh for debris removal. When this gold-plated paste arrived on the pottery and glass by screen printing and baked, the pattern with a strong white metallic gloss was obtained.

Example 6 Preparation of Palladium Gold Paste

10 parts of palladium acetylide, 20 parts of gold acetylide, 3.8 parts of octyl acid bismuth, 0.05 parts of rhodium acetylide, 8 parts of ethyl cellulose, 20 parts of ethyl lactate, and 35 parts of butyl carbitol were kneaded into paste. The finished paste was passed through a mesh for debris removal. The palladium gold paste was obtained by screen printing on a pottery and glass sheet and fired, thereby obtaining white metallic gloss palladium.

Example 7 [Preparation of Amount]

24 parts of gold acetylide, 3.3 parts of bismuth octylate, 0.048 parts of rhodium acetylide, 20 parts of kopibalsam, 45 parts of ethyl lactate, and 5 parts of DEP were stirred to form a liquid phase. The completed amount was filtered to remove debris. This amount was applied with a brush to arrive on the pottery and glass, and then fired to obtain a glossy gold pattern.

Example 8 Application of Gold Paste to Printed Thermal Head Electrodes

36 parts of gold acetylide, 3.0 parts of bismuth naphthenate, 0.036 parts of rhodium acetylide, 7 parts of ethyl cellulose, 1 part of aspart, 49 parts of butyl carbitol, and 3 parts of DEP were kneaded into paste. The finished paste was passed through a mesh to remove debris. The gold paste was patterned on ceramics by screen printing and then fired to obtain a smooth gold pattern. When this gold pattern was used as an electrode of the thermal head of a print, it turned out that it is excellent in the electrical conductivity performance.

Example 9 Application of Platinum Paste to Special Ceramics

60 parts of platinum acetylide, 8 parts of nitrocellulose, and 32 parts of butyl carbitol acetate were kneaded into a paste. The finished paste was passed through a mesh to remove debris. The platinum paste was patterned on special ceramics for semiconductor production by screen printing and then fired, thereby obtaining a smooth platinum pattern. When this special ceramics was used as an electrode of a semiconductor manufacturing apparatus, it turned out that it is excellent in electrical conductivity performance.

Example 10 Application of Gold Platinum Paste to Electronic Component Electrodes

Gold acetylide 17 parts, platinum acetylide 18 parts, octyl acid bismuth 3.3 parts, rhodium acetylide 0.072 parts, ethyl cellulose 4 parts, petroleum resin 15 parts, terpineol 20 parts, butyl carbitol 20 parts, DEP 5 parts The mixture was kneaded into a paste. The finished paste was passed through a mesh for debris removal. The gold platinum paste was patterned on a ceramics by screen printing and then fired to obtain a smooth gold platinum alloy pattern. When this pattern was used as an electrode of an electronic component, it turned out that it was excellent in the aspect of electrical conductivity performance, and also it can be used as an electrode of other electronic components.

Example 11 Application of Palladium Gold Paste to Electronic Component Electrodes

18 parts of gold acetylide, 12 parts of palladium acetylide, 5 parts of octyl acid bismuth, 0.04 parts of rhodium acetylide, 5 parts of ethyl cellulose, 17 parts of petroleum resin, 15 parts of terpineol, 25 parts of butyl carbitol, 5 parts of DEP The mixture was kneaded into a paste. The finished paste was passed through a mesh for debris removal. The palladium gold paste was patterned on ceramics by screen printing and then fired to obtain a smooth palladium gold alloy pattern. When the pattern was used as an electrode of an electronic component, it was found to be excellent in terms of electrical conductivity performance, and it could be seen that it could also be used as an electrode of other electronic components.

The present invention is not limited to the above embodiments, and various modifications, design variations, and the like are included in the technical scope within the scope not departing from the technical idea of the present invention.

Industrial use

As described above, the present invention provides a general formula M (-C≡C-R) _n (wherein M is a metal atom, n is an atom number of the metal atom M, and R contains or contains an oxygen atom). A metal acetylide compound represented by a non-hydrocarbon group), and an organic solvent and / or a resin are kneaded therein to prepare a metal composition for plating such as a metal liquid and a metal paste. Since metal acetylide compounds are easy to melt | dissolve in various organic solvents, they are suitable as a metal raw material of the metal composition for plating. Metal acetyl lead compound also does not emit pollutants, such as sulfur and does not contain a halogen element, upon firing SO _x, a halogen, an advantage that can contribute to the purification of environment. As a result, a metal film can be formed at a low price without requiring equipment equipment such as a desulfurization apparatus. When the metal liquid or the metal paste arrives at the raw material and calcined, a very smooth and dense metal film can be formed, and a high metal gloss can be obtained, so that the metal liquid or metal paste can be used for decorating ceramics or glassware. Moreover, since the electrical conductivity of this metal film is very excellent, it can be used as an electrode of an electronic component. In a metal composition containing a plurality of metal acetylide compounds, a plurality of metals may be bonded to each other to form a high performance metal film.

Claims (9)

A metal acetylide compound represented by the general formula M (-C≡C-R) _n (wherein M is a metal atom, n is a valence of a metal atom M, and R is an oxygen group with or without an oxygen atom) An organometallic liquid metal composition obtained by dissolving and dispersing a solvent in an organic solvent. A metal acetylide compound represented by the general formula M (-C≡C-R) _n (wherein M is a metal atom, n is a valence of a metal atom M, and R is an oxygen group with or without an oxygen atom) An organometallic paste-like metal composition obtained by kneading a resin and an organic solvent imparting viscosity and viscosity. The metal composition of Claim 1 or 2 which mix | blended the additive for improving the adhesiveness of the metal film after baking. The metal composition according to any one of claims 1 to 3, wherein a plurality of metal acetylide compounds having different metal elements are blended. The metal composition according to claims 1 to 4 arrives on the surface of the material in a desired pattern to form a metal composition film, and the metal composition film is heated to decompose and evaporate materials other than metal, and at the same time sinter the metal to form a dense metal film. Metal film forming method characterized in that. A material in which a metal film of a desired pattern is formed on the material surface by the method according to claim 5. 7. The material of claim 6, wherein the material is a glass tableware, porcelain or ornament. The raw material according to claim 6, wherein the raw material is an electronic component, and the metal film constitutes an electrode of the electronic component. The material according to claim 8, wherein the electronic component is a thermal head of a print.