JPH01318044A - Preparation of ruthenium resinate - Google Patents

Abstract

PURPOSE:To obtain ruthenium resinate which can be dissolved in an ordinary org. solvent and is formed into a uniform thin film by a simple operation such as coating, drying, baking, etc., by reacting an Ru compd. with an org. acid or with a mixture of an org. acid with ammonia or an amine directly or mixed with turpentine oil as a solvent. CONSTITUTION:An Ru compd., e.g., a halide, an oxide or a sulfate is reacted with an org. acid, e.g., 2-ethylhexanoic acid, octanoic acid, naphthenic acid, arom. carboxylic acids, abietic acid or a gum rosin contg. abietic acid as the main component or with a mixture of an org. acid with ammonia or an amine selected from among prim., sec. and tert. amines, e.g., n-propylamine, diethylamine or triethylamine directly or mixed with turpentine oil as a solvent and a produced oily substance is extracted with, e.g., an org. solvent (e.g., CHCl3) to remove water and thereafter the org. solvent is evaporated.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a method for producing ruthenium resinate, which is used for decoration on the surfaces of ceramic products and glass products, for electronic industry, and the like.

(Prior art and its problems) Conventionally, as a method for forming a thin film layer of noble metal for decoration or electronic industry, there is a method using a glass-containing paste.

However, the drawback is that small pores are likely to occur and the film thickness is 10J.
n is the limit, and since precious metal powder is used, the film thickness varies greatly, and when used as a resistor, etc., the effect is particularly large and becomes a problem. There is a strong desire to develop organic ruthenium compounds that are soluble and uniformly dispersed in organic solvents.

(Purpose of the Invention) The present invention has been made to solve the above-mentioned conventional problems, and forms a uniform thin film by dissolving it in a common organic solvent and performing simple operations such as coating, drying, and baking. Easy to do, and
An object of the present invention is to provide a method for obtaining ruthenium resinate using a simple manufacturing method.

(Means for Solving the Problems) The present invention is directed to the production of ruthenium resinate, which is characterized by reacting a ruthenium compound and an organic acid, or a mixture of an organic acid and ammonia or an amine, either directly or by mixing turpentine oil as a solvent. It's a method.

The present invention will be explained in more detail below.

As ruthenium compounds, fluoride, chloride, bromide,
A compound selected from iodides, oxides, sulfates, dithionates, acetates, and potassium salts is used directly or dissolved in a solvent such as water to facilitate the reaction.

The organic acid is selected from the group consisting of fatty acids such as 2-ethylhexanoic acid, octanoic acid and naphthenic acid, polynuclear fatty acids such as aromatic carboxylic acids and abietic acid, gum rosin whose main component is abietic acid, and ruthenium acetylacetonate.

As the amine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, 5ec-
Selected from the group consisting of primary amines of butylamine, tert-butylamine, n-amylamine, isoamylamine, secondary amines of diethylamine, methylethylamine, di-n-propylamine, and tertiary amines of triethylamine, tri-n-propylamine.

The above organic acid can be reacted directly with the above ruthenium compound to generate an organic ruthenium salt, but preferably, ammonia or the above amine is mixed and reacted.

As a result, ruthenium resinate can be produced using the desired simple apparatus and method, and moreover, ruthenium resinate can be obtained that dissolves uniformly in an organic solvent.

The reaction is carried out in a water bath or an oil bath, preferably under stirring to ensure uniformity and speed of the reaction.

In addition, when reacting by mixing with turpentine oil as a solvent, a commonly used reflux device is used to suppress evaporation.

An oily substance produced by reacting a combination of a ruthenium compound and an organic acid, a ruthenium compound and an organic acid and ammonia or amine, a ruthenium compound, an organic acid, and turpentine oil, etc. (If there is a precipitate, filtration may be performed. ) is extracted into an organic solvent, the water is dehydrated using an anhydrous inorganic salt, etc., and the organic solvent is evaporated to obtain ruthenium resinate.

Moreover, it can also be used in a state extracted with an organic solvent.

Examples of the ruthenium resinate according to the present invention will be described below, but the examples are not intended to limit the present invention.

(Example 1) 2-Ethylhexanoic acid (0.7 mol, 100.9 g) and triethylamine (0.7 mol, 70.83 g) are mixed.

Separately, ruthenium trichloride (Contains 45% Ru, 39.3g)
Dissolve in 150 mj2 of water.

This ruthenium trichloride solution was mixed with a mixed solution of 2-ethylhexanoic acid and triethylamine, and the mixture was reacted with stirring in a water bath at a temperature of 80° C. for 6 hours.

After the reaction, the resulting oily substance was extracted using chloroform as an organic solvent, dehydrated and dried over anhydrous sodium sulfate, and the organic solvent was heated and evaporated at a water bath temperature of 60°C to form an oily ruthenium resinate (dark green). ) 80.47g was obtained.

When the ruthenium resinate was analyzed, the ruthenium content was 20.0%.

Calculating the yield as ruthenium from this result, it is 9
It was 1%.

(Example 2) Ruthenium oxide (I'V) (0.32 mol, 42.
6 g), gum rosin (96.8 g) and turpentine (1
00mj were mixed and reacted for 2 hours at an oil bath temperature of 170°C with stirring under a reflux device. After the reaction, chloroform was added and extracted, and the obtained chloroform extract was filtered at a water bath temperature of 60°C. By heating and evaporating, 68.12 g of petroleum-like ruthenium resinate (dark green) was obtained.

When the ruthenium resinate was analyzed, the ruthenium content was 19.0%.

Calculating the yield as ruthenium from this result, it is 4
It was 0%.

(Example 3) Using the ruthenium resinates obtained in Examples 1 and 2 as organic solvents, 4 g/10 mj each of menthanol, terpineol, and dibutylcarpitol were added! When dissolved, it became a homogeneous solution.

The solution obtained above was coated on a ceramic substrate, dried at room temperature, heated at 300°C for 5 minutes, and heated to 700°C.
When fired at ℃, a black, dense thin film without small pores was obtained.

When this film was analyzed, ruthenium and oxygen were detected.

(Effects of the Invention) The present invention provides a material that can be dissolved in a general organic solvent that can compensate for the drawbacks of conventionally used pastes as a raw material for forming noble metal thin film layers that have a particularly wide range of uses in the electronic industry. Furthermore, by being able to produce ruthenium resinate with a high ruthenium content, it has become possible to form highly reliable thin films not only for use in the electronics industry but also by taking advantage of the properties of the precious metal, which will greatly contribute to the development of technology. .

(Embodiments) The present invention has the features described in the claims, and examples of embodiments thereof are as follows.

2. The method for producing ruthenium resinate according to claim 1, wherein the ruthenium compound is selected from the group consisting of fluoride, chloride, bromide, iodide, oxide, sulfate, dithionate, acetate and potassium salt.

3. A claim in which the organic acid is selected from the group consisting of fatty acids such as 2-ethylhexanoic acid, octanoic acid/naphthenic acid, polynuclear fatty acids such as aromatic carboxylic acid and abietic acid, gum rosin whose main component is abietic acid, and ruthenium acetylacetone. Item 1 or the method for producing ruthenium resinate according to Embodiment 2.

4. The amine is primary amine of n-propylamine, isopropylamine, n-butylamine, isobutylamine, 5ec-butylamine, tert-butylamine, n-amylamine, isoamylamine, diethylamine, methylethylamine, di-n-propylamine. The method for producing a ruthenium resinate according to any one of claims 1 to 3, wherein the ruthenium resinate is selected from the group consisting of tertiary amines such as primary amines and tertiary amines such as triethylamine and tri-n-propylamine.

Applicant: Tanaka Kikinzoku Kogyo Co., Ltd.

Claims (1)

[Claims] 1. A method for producing ruthenium resinate, which comprises reacting a ruthenium compound and an organic acid, or a mixture of an organic acid and ammonia or an amine, either directly or by mixing turpentine oil as a solvent.