WO1999027159A1

WO1999027159A1 - Metal composition containing metal acetilide, blank having metallic coating formed therewith, and method for forming the metallic coating

Info

Publication number: WO1999027159A1
Application number: PCT/JP1998/005139
Authority: WO
Inventors: Akio Harada; Yoshiki Okamoto
Original assignee: Daiken Chemical Co., Ltd.
Priority date: 1997-11-26
Filing date: 1998-11-13
Publication date: 1999-06-03
Also published as: EP0976848B1; EP0976848A1; TW561140B; KR20000069225A; DE69840542D1; JPH11158184A; JP3491021B2; EP0976848A4

Abstract

A metal composition such as metallic fluid or metallic paste is prepared by compounding a metal acetilide represented by the general formula M(-C C-R)n (wherein M is a metallic atom, n is the valency of the atom M, and R is a hydrocarbon group optionally bearing oxygen) as an organometallic source with a resin and an organic solvent and kneading the mixture. When the composition is applied in a desired pattern to a required portion of a decorative article, such as porcelain or glass, or an electronic part and at least the required portion is dried and heated, the organic substances except for the metal are decomposed and released and only the metal is sintered in the required pattern.

Description

Akira Itoda A metal composition containing a metal acetylide compound, a material on which a metal film is formed using the metal composition, and a method for forming the metal film

(Technical field)

The present invention relates to a metal composition for forming a metal film such as an electrode or a decorative film on the surface of a material and a method of applying the same, and more particularly, to a method for converting a metal acetylide compound containing no sulfur or halogen into an organic compound. TECHNICAL FIELD The present invention relates to a metal composition which does not generate harmful gases to the environment such as SO _x and C 1 when firing a metal film to be used as a metal agent, and which can maintain the environment cleanly and a method of applying the same. (Background technology)

Normally, when electrodes are formed on an insulating substrate or an electronic component, a metal powder or an organic metal complex is mixed and kneaded with a resin, an organic solvent, etc. to prepare an organic metal paste, and the second organic metal paste is prepared. The strip is applied to electronic components on a circuit board by screen printing or the like to form a predetermined circuit pattern, and this pattern is heated to decompose organic components. There is known a method of evaporating and depositing a metal in a film form. In addition, when forming a decorative metal film on the surface of pottery or the like, a metal solution having low viscosity is required, and an organic metal complex that is soluble in an organic solvent is selected. An organic metal liquid is prepared by dissolving and dispersing in the organic solvent. As described above, organometallic complexes are currently used in a wide range of fields such as electronic equipment, ceramics, and crafts.

Conventionally, as a organometallic complexes have been have use in such applications this, Pa Rusa beam based compound, eg if sulfide Te Le Binet ol gold _{(C:. H, s SA} u C 1,), vulcanized I匕Te Le Binet Haut Le platinum _{(C,. H, B SP} t C 1,), sulfide Te Le Binet per Rupa

I one Radium (C! OH! S SP d Clx) is known. C These compounds are generally abbreviated as gold balsam, platinum balsam, and palladium balsam. In addition, precious metal balsams such as rhodium balsam and ruthenium hum are known.

The following problems remain in using these conventional balsam compounds as a base for metal compositions such as metal pastes and metal liquids.

First, when attempting to deposit a metal using these metal compositions, the on-process firing step cannot be avoided. Since balsam compounds contain chlorine and sulfur, they are inevitably generated as by-products such as S0 and C1 in the firing process. The release of these harmful substances into the environment not only adversely affects the hygiene of workers, but also has a negative effect on the natural environment in general. In addition, a large amount of equipment such as a desulfurization unit was required to recover these harmful substances, and it was difficult to recover 100% of the harmful substances. Since SOx and halogen are also causes of damage to the baking equipment, a metal composition for forming a safer metal film has been desired.

Second, SO and halogen generated during firing may adversely affect the material. The material is ripened to decompose and evaporate components other than metal.However, sυ and halogens corrode the material, and sulfur and halogen atoms become impurities in the material. May spread. In particular, when the material was an electronic component, the electronic properties were sometimes adversely affected.

Third, when preparing an organometallic liquid from a balsam-based compound, there are limitations on the organic solvents that can be used. For example, it is highly soluble in aromatic solvents, but hardly soluble in alcohol solvents. In addition, there are similar restrictions on the resins required for preparing an organic metal paste. For example, if the resin is nitrocellulose, it is soluble in solvents such as butyl carbitol and butyral carbitol acetate, but terbineol Not necessary for is there. Therefore, when the solvent is restricted on the organometallic complex side, the resin that can be used is naturally restricted, so that the types of metal bases that can be prepared are restricted, and their uses are also restricted. become.

(Disclosure of the Invention)

The present invention has been made in order to improve the above-mentioned drawbacks, and uses a metal acetylide compound containing no sulfur or chlorine as an organometallic complex which is a main component of a metal composition. Suggest and. This metal acetylide compound has a general formula M (— C ≡ C 1 R), where M is a metal atom, n is the valence of the metal atom M, and R is an oxygen atom-containing compound. Hydrocarbon group), and does not contain sulfur or halogen as a constituent element.

The present invention proposes a metal composition in which the metal acetylide compound is dissolved and dispersed in an organic solvent to make an organic metal liquid. The present invention proposes a metal composition obtained by kneading the metal acetylide compound, a resin for adjusting viscosity, and an organic solvent to form an organic metal paste. We propose a metal composition containing an additive that enhances the adhesion of the metal film. In addition, a metal composition in which a plurality of metal acetylide compounds having different metal elements are combined is proposed.

These metal compositions are applied 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 substances other than metals. At the same time, we propose a metal film formation method that forms a dense metal film by sintering the metal. We propose a material with a metal film of the desired pattern formed on the surface by this method.

The present inventors have conducted intensive studies on organometallic complexes that do not contain sulfur or halogens that cause environmental pollution and are soluble in many organic solvents, and as a result, a type of acetylene derivative It has been found that such a metal acetylide compound is suitable for the purpose of the present invention, and based on this knowledge, the present invention has been accomplished. That is, the organometallic complex used in the present invention is a metal acetylide compound represented by the general formula M (-C≡C-R). In this single branch, M represents a metal atom, for example, B i, C u, In, N i, R u, R h, P d, A g, O s, I r, P t , Au, etc. As a metal composition such as an organic metal liquid or an organic metal paste, a highly stable noble metal is often used. Here, the noble metal includes Au, Ag, and platinum group (Ru, R h, P d, O s, I r, P t).

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

Ligand of metal acetylide compound—R in C≡C—R is a hydrocarbon group containing or not containing an oxygen atom, and its constituent elements are C and H, or C, H, and O You. The hydrocarbon group R desirably has 1 to 8 carbon atoms, and accordingly, the ligand as a whole preferably has 3 to 10 carbon atoms. The reason is that if the number of carbon atoms is small, the metal acetylide compound becomes difficult to dissolve in the solvent, and at the same time, the explosive property becomes large and the handling becomes dangerous. As the number increases, the weight of the metal in the substance becomes relatively small, and it becomes impossible to form a metal film when using an organic metal liquid or an organic metal base. In other words, when the metal acetylide compound of the present invention is used for a metal composition, a metal weight that is soluble in a solvent and that is constant is required. In other words, when the number of carbon atoms of the ligand C CC 数 R is in the range of 3 to 10, the metal acetylide compound is easily soluble in the solvent, and the power and the metal weight are relatively large. Thus, it can be sufficiently used as a metal composition.

When the hydrocarbon group R contains oxygen, it contains an aliphatic hydrocarbon group as a hydroxyl group when it contains oxygen, and in this case, it may be linear or may have a side chain. You may. As specific examples of the ligand C 一 C R R, H — C ¾ C R R in the form of ropin, 2 プ propyl 1 1 1 ォ 1 ブ 1 ブ 3 オ, 3 — Methyl 1 — Butine 1 3 — All, 3, 3 — Dimethyl 1-1 -butyl, 1-Bentin, 1 — Pentin 1 3-4 4 — Pentin 1 1 — E

4—Ventin 1 2—O 4 1 Methyl 1 1—Pentin, 3—Met 1 1 Ventin 1 3—Owl, 3, 4—Dimethyl 1 Pentin — 3 — O 1 — Hexin, 1 Kisin 1 — 3 — O 1 5 — Hexin 1 1 — O 1, Re, 5 — Metino 1 Kisin, 5 — Methyl 1 — hex 1 3 — all, 3, 5 — dimethyl 1 ix 1 3 — all, 1 butyl, 1 heptin 1 — 3 — all , 5-heptin 1-3-all, 3, 6-dimethyl-1-1 octin 3-all, 1-octin, 1-octin-3-o There is a certain strength S.

Further, when the hydrocarbon group R contains oxygen, there is a hydrocarbon group containing at least a cyclic hydrocarbon contained as a hydroxyl group. This hydrocarbon group may have a cyclic hydrocarbon group in a straight chain or may have a cyclic hydrocarbon group in a side chain-as a matter of course, the entire R is a cyclic hydrocarbon group. Including the case of hydrogen. As a specific example of the ligand C 3 C—R, H—C 3 C—R is in the form of 1—ethyl 1-cyclobromo 1—ethyl 1 1 — cyclobutano 1 — echini 1-cyclopentanol, 1 echini i-cyclohexano 1 — propyne 1 3 — ci Cloblobanol, i-propyne 13 — cyclobutanol, 11-propyne 13 — cycloventanol 1-butyne 14 — Cyclopropanol 1-butyne 1 4 — Cyclopropanol 1, pentin 1 5 — Cyclopropanol 1

As described above, the metal acetylide compound according to the present invention is composed only of a metal element, carbon, hydrogen, and / or oxygen, and even if it is decomposed by calcination, it is a gas. As a result, carbon dioxide, water vapor, and other parts depend on the firing temperature. Only hydrocarbons are produced, but no harmful substances such as s O and halogen gas are produced: Therefore, organometallic complexes that are extremely safe and clean for the environment and organisms It is.

Engaging Ru metal composition invention organometallic liquid and are classified as organometallic-Based Ru ₌ organometallic liquid also to a and the metal § isethionate Li de compound Ru der organometallic complex dissolved in an organic solvent 'is dispersed It is a normal liquid. The organometallic paste is a mixture of a gold acetylide compound and a resin for viscosity adjustment in an organic solvent, and the viscosity is increased or decreased depending on the usage. You. The liquid metal composition having low viscosity may be referred to as an organometallic liquid or an organometallic base, and the boundary between the two cannot be clearly defined.

Unlike conventional balsam compounds, metal acetylide compounds are soluble in a wide range of organic solvents, both polar and non-polar. Specific examples of the organic solvent include petroleum-based solvents, esters such as terbineol, petal carbitol, and ethyl lactate, and cellosolve. , Alcohols, aromatics, and DEP (jetiphthalate).

The viscosity of the organometallic base differs depending on the application conditions (printing conditions) to the material, the firing conditions and the surface state after firing, and a resin is mixed in to adjust the viscosity. The resin is required to be easily dissolved and dispersed in an organic solvent together with the metal acetylide compound. Since metal acetylide compounds dissolve well in many organic solvents, the choice of resins that can be dissolved and dispersed in these organic solvents is much wider than conventional balsam compounds. It becomes: For example, ethylcellulose, nitroselorose, asphalt, butyral, acrylocobalms, dan Equally, these related substances can be used as resin.

The above-mentioned metal acetylide compound and an organic solvent are mixed to produce an organic metal liquid. In this case, the metal acetylide compound is 60 to 10 parts by weight, The organic solvent is desirably 30 parts by weight to 90 parts by weight, and it is preferable to add 10 parts by weight to 1 part by weight of an additive described later thereto. 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 so small that a metal film cannot be formed, and when the amount is larger, the metal acetylide compound becomes organic. It cannot be dispersed in the solvent and precipitates. Therefore, an organometallic liquid having a favorable range can be provided. The optimum blending amount can be set according to the conditions such as the material for forming the metal film, the ripening temperature, and the film thickness. In addition, a metal acetyl compound, an organic solvent and a resin are mixed to produce an organic metal base. In this case, the compounding amounts of the components are 60 to 10 parts by weight for the metal acetylide compound, 30 to 85 parts by weight for the organic solvent, and 3 to 30 parts by weight for the resin. Department is desirable. If necessary, the additives can be added in an amount of 1 to 10 parts by weight.

The viscosity of the organometallic base produced in this range is in the range of 5 Op (poise) to δ0000p (poise). When the viscosity becomes lower than the lower limit, the organic metal base approaches the organometallic liquid, and when the viscosity becomes higher than the upper limit, the metal composition is applied to the surface of the material. It will be difficult to reduce the thickness of the metal paste .. The viscosity of the organometallic paste can be changed independently according to the application. To produce an organometallic liquid or organometallic paste, select the necessary components from metal acetylide compounds, organic solvents, resins, and additives, and fill the container with the required weight. Then, it is uniformly dissolved and dispersed using a kneading device. This mixture is passed through one or more stages of mesh to remove tiny particles. As a result, finely and uniformly dissolved and dispersed organometallic solution, organometallic solution is removed. You can get Metal acetylide compounds are much easier to dissolve in organic solvents than conventional organometallic complexes, and therefore have the advantage of obtaining a metal composition that is uniformly dissolved and dispersed in the simple kneading and stirring step. Has: Material using organometallic liquid or organometallic paste manufactured by the above process A metal composition film is formed on the surface. There are various types of materials, and the present invention covers not only specific products but also a very wide range of products. For example, there are decorative items such as ceramics, tiles, and glass products, as well as electronic components, such as electrodes for a printer's general head.

In order to form a metal composition film of a predetermined pattern on a material surface with an organic metal liquid, there are simple writing and dipping methods. In the case of a metal sheet, there are methods such as screen printing, pad printing, transfer, and dipping.

Next, the metal composition film is fired to form a metal film. The entire material may be put into a heating furnace and heated to the firing temperature, or the metal composition film on the material surface may be locally heated with a gas burner or the like. During firing, ligands other than metals in organic solvents, resins, additives, and metal acetylide are thermally decomposed and evaporated, and the remaining metal atoms bond and grow with each other. Form a metal film. The metal film functions as a decoration film in a decorative product, and functions as an electrode in an electronic component.

The metal composition of the present invention has the following features. First, because it does not contain sulfur or chlorine, it does not emit harmful substances such as SOx and halogen during the firing stage, is environmentally clean, and requires no equipment such as desulfurization equipment. Become. Second, the decomposition temperature of the metal acetylide compound is about 400 degrees, which is slightly lower than the decomposition temperature of the conventional organometallic complex. In other words, since it can be fired at a relatively low temperature of 400 ° C. or more, it can be applied to many materials such as low-melting glass, and can prevent deterioration and thermal denaturation of the material. You.

Third, the fired metal film can be finished smoothly like a mirror surface, and can be used in fields where high precision is required, such as decorative parts, as well as electronic parts.

(Best mode for carrying out the invention)

The best mode for carrying out the present invention will be described below as an embodiment. Example 1 [Preparation of gold paste]

Gold acetylide 40 parts, naphthenic acid bismuth 0.8 parts, rhodium acetylide 0.08 parts, ethylcellulose 6 parts, terbione When thirty-eight parts were kneaded, they became paste-like. The resulting paste was passed through a mesh to remove debris. When this gold paste was applied on pottery and glass by screen printing and then fired, a shiny golden pattern was obtained.

Example 2 [Preparation of gold list]

Gold acetylide 40 parts, naphthenic acid bismuth 5.5 parts, rhodium acetyl chloride 0.08 parts, nitrocellulose 5 parts, butinole cane bite 39 When 9 parts were kneaded, it became paste-like. This base was passed through a mesh to remove debris. When this gold paste was applied to pottery and glass by screen printing and then baked, a shiny golden pattern was obtained.

Example 3 [Preparation of gold and silver base]

40 parts of gold acetylide, 5.5 parts of bismuth octylate, 10 parts of silver acetylide, 0.1 part of rhodium acetylide, 4 parts of ethylcellulose, lactic acid Kneaded with 15 parts of ethyl and 20 parts of butyl carbitol in the form of a roll; remove the dust by passing the roasted paste through a mesh did. When this gold and silver paste was applied to pottery and glass by screen printing and then baked, a pattern with strong gold luster was obtained.

Example 4 [Preparation of gold paste]

14 parts of gold acetylide, 2.0 parts of bismuth octinoleate, 0.7 part of silver acetylide, 0.028 parts of rhodium acetylide, 6 parts of ethylcellulose, 2 parts When kneaded with 4 parts of cellulose acetate, 30 parts of ethyl lactate and 40 parts of butyl carbitol, it became paste-like. The finished paste was passed through a mesh to remove debris. This gold paste is screen printed by screen printing. When applied and baked on the glass and glass, a shiny golden pattern was obtained.

Example 5 [Preparation of gold platinum base]

12 parts of platinum acetylide, 19 parts of gold acetylide, 3.3 parts of bismuth octylate, 0.04 part of rhodium acetyl chloride, 8 parts of ethylcell mouth, 8 parts of lactic acid When 20 parts of ethyl and 35 parts of butyl carbitol were kneaded, the mixture became pasty. The finished paste was passed through a mesh to remove debris. This gold-platinum paste was applied on ceramics and glass by screen printing and baked. As a result, a pattern with strong white metallic luster was obtained.

Example 6 [Preparation of palladium gold paste]

10 parts of palladium acetylide, 20 parts of gold acetylide, 3.8 parts of bismuth octylate, 0.05 part of rhodium acetyl chloride, ethylcellulo When 8 parts of base, 20 parts of ethyl lactate and 35 parts of butyl carbitol were kneaded, the mixture became a base. The resulting paste was passed through a mesh to remove debris. When this palladium gold base was applied on ceramics and glass by screen printing and baked, a pattern with a white metallic luster was obtained.

Example 7 [Preparation of gold solution]

24 parts of gold acetylide, 3.3 parts of bismuth octoate, 0.048 parts of rhodium acetylide, 20 parts of kopaibanolesam, 45 parts of ethyl lactate, 5 parts of DEP When stirred, it became liquid. The resulting gold liquor was filtered to remove debris. When this gold solution was applied to pottery and glass by brush painting and then baked, a shiny golden pattern was obtained.

Example 8 [Application of Gold Paste to Printer / Head Head Electrode-]

36 parts of gold acetylide, 3.0 parts of bismuth naphthenate, 0.036 parts of rhodium acetylide, 7 parts of ethyl cenorylose, asphal Part 1, Petit Norre After mixing 49 parts of carbitol and 3 parts of DEP, the resulting paste became a paste.The finished paste was passed through a mesh to remove debris. . When this gold paste was patterned on ceramics by screen printing and then baked, a smooth gold pattern was obtained. When this gold pattern was used as the electrode of the thermal head of the printer, it was found that it was excellent in terms of electric conduction performance.

Example 9 [Application of platinum paste to special ceramics]

When 60 parts of platinum acetylide, 8 parts of nitrose cellulose, and 32 parts of butyl canolebitol acetate were kneaded, a paste was formed. The resulting paste was passed through a mesh to remove debris. If this platinum paste is patterned on a special ceramic for semiconductor manufacturing by screen printing and then fired, a smooth white gold pattern can be obtained. Was. It has been found that when this special ceramic is used as an electrode of a semiconductor manufacturing apparatus, the electric conduction performance is improved.

Example 10 [Application of gold-white gold paste to electronic component electrode]

17 parts of gold acetylide, 18 parts of white gold acetylide, 33 parts of bismuth octylate, 0.072 parts of rhodium acetylide, ethylcellulose When 4 parts, 15 parts of petroleum-based resin, 20 parts of terbineol, 20 parts of butylcarbitol and 5 parts of DEP were kneaded, a paste was formed. The finished paste was passed through a mesh to remove debris. This gold-white gold paste was patterned on ceramics by screen printing and then fired. The pattern was obtained. When this pattern was used as an electrode for electronic components, it was found that it was excellent in terms of electrical conduction performance, and it could be used as an electrode for other electronic components. I understood that.

Example 11 1 [Application of palladium gold paste to electronic component electrode] 18 parts of gold acetylide, 12 parts of palladium acetylide, bis (octylate) 2.5 parts of mass, 0.4 parts of rhodium acetylide, 5 parts of ethylcellulose, 17 parts of petroleum resin, 15 parts of tervineol, 25 parts of butyl carbitol, When 5 parts of DEP were kneaded, it became paste-like. The finished paste was passed through a mesh to remove debris. This palladium gold paste was patterned on ceramics by screen printing and then baked, resulting in a smooth palladium gold alloy pattern. Was obtained. When this pattern was used as an electrode of an electronic component, it was found that it was excellent in terms of electrical conduction performance, and that it could be used as an electrode for other electronic components. I got it.

The present invention is not limited to the above-described embodiments, but includes various modifications and design changes within the technical scope thereof without departing from the technical idea of the present invention. .

(Industrial use)

As described in detail above, the present invention provides, as a metal source, a general formula M (—C≡CR) „(where M is a metal atom, n is a valence of the metal atom M, and R is an oxygen atom. A metal acetylide compound represented by (with or without a hydrocarbon group), and kneaded with an organic solvent and / or resin to form a metal liquid or a metal base. Since the metal acetyl compound is easily dissolved in various organic solvents, it is suitable as a metal raw material for the metal composition for a metal. In addition, since this metal acetylide compound does not contain sulfur and halogen elements, it does not release environmental pollutants such as SO and halogen during firing. As a result, it has the advantage of contributing to environmental cleanup, thereby eliminating the need for equipment such as desulfurization equipment. If this metal liquid or metal paste is applied to a material and then baked, an extremely smooth and fine metal film can be formed, and a high-grade metal film can be formed. Since it shows luster, it can be used for decoration of ceramics and glassware. Furthermore, since the electrical conductivity of the metal film is extremely good, it can be used as an electrode for electronic components. In addition, in a metal composition containing a plurality of metal acetylide compounds, a plurality of metals can exhibit their advantages and form a high-performance metal film.

Claims

The scope of the claims

1. A metal represented by the general formula M (— CC-R) „(where M is a metal atom, n is the valence of a metal atom M, and R is a hydrocarbon group containing or not containing an oxygen atom). A metal composition in which an acetylide compound is dissolved and dispersed in an organic solvent to form an organometallic liquid.

2. General formula M (-C≡C-R) „(where M is a metal atom, n is the valence of metal atom M, and R is a hydrocarbon group containing or not containing an oxygen atom). A metal composition obtained by kneading a metal acetylide compound to be used, a resin for adjusting viscosity, and an organic solvent to form an organic metal paste.

3. The metal composition according to claim 1, further comprising an additive that enhances the adhesion of the metal film after firing.

4. 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.

5. A metal composition film is formed by applying the metal composition according to claims 1 to 4 on a surface of a material in a desired pattern, and heating the metal composition film to remove substances other than metal. A method for forming a metal film, comprising decomposing and evaporating and simultaneously sintering a metal to form a dense metal film.

6. A material having a metal film of a desired pattern formed on the surface of the material by the method according to claim 5.

7. The material according to claim 6, wherein the material is glass tableware, ceramics, or a decorative item.

8. The material according to claim 6, wherein the material is an electronic component, and the metal film forms an electrode of the electronic component.

9. The material according to claim 8, wherein the electronic component is a thermal head of a printer.