JPS6262824A - Production of polymerized thin film of metalphenanthroline complex - Google Patents

Abstract

PURPOSE:To obtain the titled thin film having high toughness, insoluble in solvent and useful as an indicator, display element, etc., by evaporating and polymerizing a metal-containing compound with a phenanthroline compound in a low-temperature gas plasma thereby depositing a polymerized thin film of the complex of both compounds on a substrate. CONSTITUTION:A metallic compound (e.g ferrocene) and a phenanthroline compound (e.g. o-phenanthroline) are evaporated and polymerized in a low- temperature gas plasma of preferably a non-polymerizable gas (e.g. nitrogen) in vacuum of preferably 10<-3>-10<0>Torr by heating e.g. with a heaer, far infrared radiation, etc. to form the objective polymerized thin film of metal- phenanthroline complex on a substrate (e.g. cellulose acetate membrane filter, etc.). The metal-containing compound is preferably an organometallic compound and the metal is preferably Cu, Ag, Cd, Sn, Pb, Mn, Fe, Ni, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a method for producing a metal-phenanthroline complex polymeric thin film.

<Prior art> Phenanthroline, especially O-phenanthroline, contains Fe,
Ag, Cd, Cu, Zn, lAn, Pb, Sn, Ni
It forms chelates with other metals and has been used for metal analysis and recovery.

Furthermore, it is known that the color of the complex of the metal phenanthroline hull changes depending on the charge of the central metal. for example,
In the iron-phenanthroline complex, the color of the complex changes due to the oxidation/reduction reaction shown in the formula below.

Fe (0-phenanthroline) R+e, -colorless
Fe (0-phenanthroline) 8 Red Therefore, this oxidation/reduction reaction is caused electrically.

It can cause electrochromism. If gold k.
If a thin film of phenanthroline is made, electrochromatography 6
It can be used as a pick element.

Up to now, no attempt has been made to make metal/phenanthroline thinner, let alone MU.

<Problems to be Solved by the Present Invention> As a result of intensive research, the present inventors have completed the present invention. The object of the present invention is to provide a method for industrially and inexpensively manufacturing Heqong Meditation.

<Means for solving the problems> The method of the present invention vaporizes and polymerizes a metal-containing compound and a phenanthroline compound in a hot gas plasma to form a polymerized thin film of a gold-phenanthroline complex on a substrate. It is characterized by forming.

The low-temperature gas plasma used in the method of the present invention refers to non-equilibrium plasma in which the electron temperature in the plasma is sufficiently higher than the temperature of ions or other active atoms, and any known method may be used to generate the plasma. For example, J-R, Hollahan and A-'I
', Bell edition "Application Technology of Plasma Chemistry"
, Wiley, New York 1974 and M Zien (S
hen) "Plasma Chemistry of Polymers", Detzker, New York, 1976. That is, the monomer can be placed under vacuum between parallel plate electrodes connected to a high frequency generator, and the plasma can be generated using the parallel plates either outside or inside the vacuum chamber. Alternatively, an electric field may be created by an external induction coil to generate a plasma of ionized gas, or a plasma may be generated by placing oppositely charged electrodes spaced apart directly into a vacuum chamber.

The gas for the low-temperature gas plasma is preferably a non-oxidizing and non-polymerizable gas, such as nitrogen, argon, helium, hydrogen, etc. The amount of non-polymerizable gas is determined so that the degree of vacuum in the reactor is normally 10'' to 102 torr, preferably 1
0-4 to 10' torr, more preferably 1σ8 to
Set to 10°torr. Vacuum degree is 1O-
If it is less than 6 torr or more than 102 torr, generation of low-temperature gas plasma becomes difficult or unstable, which is not preferable.

Low-temperature gas plasma can be easily generated by applying high frequency. The high frequency output to be applied has an iα pole shape, t
It depends on the area of the a electrode, the size of the reactor, etc., but the diameter is 15
When using parallel plate electrodes, the power is usually 200W or less,
Preferably 5 to 150W, more preferably 10 to ioo
w, particularly preferably 20 to 70W.

The plasma polymerization time can be appropriately selected depending on the purpose, but is usually 3,600 seconds or more, preferably 10 to 600 seconds, and most preferably about 30 to 300 seconds. Furthermore, in a low-temperature gas plasma that is mainly composed of air or an oxidizing gas such as an acidic gas, the monomer is likely to be oxidized in the plasma, making it difficult to form a single composite film. Metal-containing compounds are ++lh in terms of plasma polymerized film properties, ease of formation, and ease of vaporization.
Metal compounds are preferred. In addition, the type of metal must be one that has only the ability to form a complex with phenanthroline, and is preferred. Cu, Ag, Cd, 3n
, Pb, Mn, F"e, Ni, etc.

There are three isomers of phenanthroline: 0-, m-, and p-phenanthroline, but 0-phenanthroline (
1,10-phenanthroline) and derivatives thereof are preferred. Although O-phenanthroline has a boiling point of 360° C. or more at normal pressure and a low vapor pressure, it is preferable to use various derivatives to facilitate vaporization and to improve the surface on which the plasma polymerized film is formed.

Metal-containing compounds and phenanthroline are 10-6 to 10
They cannot be vaporized even under a pressure of 2 tbrr, so in order to form a good plasma polymerized film, it is necessary to heat them and actively vaporize them. Heating methods include heater heating, far infrared heating, high frequency heating, laser heating, and heating with an electron gun.

The evaporation rate of the metal-containing compound and phenanthroline is preferably equal to or higher than the formation ratio of the metal phenanthroline complex. If there is a lack of metal, complex formation will not be sufficient.

When a metal-containing compound and phenathroline are vaporized and polymerized in a low-temperature gas plasma, a solvent-insoluble metal phenanthroline complex thin film is formed, and a good crosslinked polymer film is formed. Although the formation process of this thin film of gold or 4-functional nanthroline complex has not been fully elucidated, the metal ions of the metal-containing compound and the active molecules of phenanthroline can move freely in the sparse space of vacuum in the plasma. It is thought that the metal phenanthroline complexes are recombined to form a polymerized thin film of the metal phenanthroline complex.

<Effects of the Invention> The method of the present invention has great industrial significance in that it provides a method for producing a metal-phenanthroline complex polymerized thin film, which has not been obtained at all heretofore.

In addition, the color of the metal-phenanthroline complex polymer thin film obtained by the method of the present invention changes depending on the type of central metal and the number of charges 12, and this can be used to produce useful oxidation/reduction indicators and colorimetric indicators 1 Display element pre-preparation has many useful properties, such as being able to be used as a test strip.

<Example> EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to Examples.

Example 1 FIG. 1 shows a plasma reactor used in the present invention. 1
is a high frequency power source (RFtf source) that generates high frequency waves of 13.56 MHz. The high frequency waves generated in the reactor 2 are passed through 19 matching boxes to the electrode 3 having a diameter of 1Ocrn in the reactor 2. When a high frequency wave is applied between the electrode 3 and the earth-side electrode 5, a low-temperature gas plasma is generated within the reactor. Using ferrocene as the metal-containing compound, 1. I put Of. Moreover, 0.51 of phenanthroline was placed in the heating container. Slightly open the valve 11, flow nitrogen gas at a rate of 15 ml/min, start the vacuum pump 9, and
? The inside of the reactor was evacuated at a pumping speed of 0.000. A low-temperature gas plasma of nitrogen gas is generated by applying a high frequency wave with an output of 30 W at a vacuum level of 1 Torr. The heating power source 22 was adjusted while generating low-temperature gas plasma, and ferrocene and phenanthroline were vaporized for 3 minutes. The amount of evaporation of ferrocene was 0.24f, and the amount of evaporation of phenanthroline was 0.719.

As the substrate 4, a cellulose acetate membrane filter having pores of 0.1 μm was used. A good thin film of iron/phenanthroline complex polymerization was obtained on the substrate. The film was reddish and was insoluble in phenanthroline solvents such as water and ethanol, confirming the formation of a thin film of iron(1) phenanthroline complex polymerization.

[Brief explanation of the drawing]

Figure 1 shows an example of a plasma polymerization apparatus. 1 is a h-frequency power source, 2 is a cross-tube reaction vessel, 3 and 5 are parallel plates tl171Th, 9 is a vacuum pump, 16.17
and 18 represent a non-polymerizable gas supply system, and 2o represents a monomer. The base body 4 is positioned almost directly above the heating container 21. 〃 Katana Fugaku Wase Meitai Shikiku Figure 1 zO: Kenomah

Claims (6)

[Claims] (1) A metal-containing compound and a phenanthroline-based compound are vaporized and polymerized in a low-temperature gas plasma, and the metal-containing compound and phenanthroline compound are polymerized on a substrate.
A method for producing a metal/phenanthroline complex polymerization thin film, which comprises forming a phenanthroline complex polymerization thin film. (2) The method according to claim 1, wherein the low-temperature gas plasma is a non-polymerizable gas plasma. (3) The method according to claim 2, wherein the non-polymerizable gas is argon, nitrogen, and helium. (4) The method according to claim 1, wherein the metal-containing compound is an organometallic compound. (5) The metal of the metal-containing compound is Cu, Ag, Zn, Cd
, Sn, Pb, Mn, Fe and Ni. (6) The method according to claim 1, wherein the phenanthroline compound is O-phenanthroline (1,10-phenanthroline) and its derivatives.