JPH04397A - Formation of thin film due to micelle electrolyzing method - Google Patents

Abstract

PURPOSE:To form a uniform organic or inorganic thin film excellent in smoothness by dispersing the nonaqueous organic or inorganic substance in a micelle soln. and making it colloidal and performing electrolysis at puncture potential or more of micelle and electrodeposition potential or below and then performing electrolysis at electrodeposition potential or more. CONSTITUTION:The nonaqueous or hardly water-soluble organic or inorganic substance is dispersed in the micelle soln. of a surfactant which has the characteristics charged by electrolysis and made colloidal. Furthermore a supporting electrolyte and electrodeposition liquid are dissolved in this micelle soln. A resin prepolymer and a cross-linking agent are made copresent and utilized as the component of this electrodeposition liquid. An organic or inorganic film is formed on a formed color pigment film by performing a first electrolysis at puncture potential or more of micelle and electrodeposition potential or below. Polymers are formed between fine particles of the organic or inorganic film by performing a second electrolysis at electrodeposition potential or more for a short time. Furthermore the operation is repeatedly performed in accordance with necessity. Thereby the particulate film formed of organic or inorganic substance is uniformly formed which is good in adhesive property and excellent in smoothness.

Description

[Detailed Description of the Invention] [Industrial Field of Application] The present invention is for forming a thin film of water-insoluble or ni@-based organic or inorganic material on an electrode by an electrochemical method. For example, if an organic dye is used as the above-mentioned substance, the electrodes can be colored with RlG or B, and the electrodes can be applied to color filters used in liquid crystal displays. In addition, due to the properties of the above substances, they can be used in various fields such as manufacturing organic semiconductors, solar cells, electrophotographic photoreceptors, PHB memories, photoelectric conversion elements, gas sensors, biosensors, piezoelectric elements, dielectrics, superconductors, etc. Application development is possible.

[Prior Art] There has been no method of forming water-insoluble or poorly water-soluble organic or inorganic particles on an electrode in an aqueous solution.

As a wet method for forming an organic film, an LB film and an electrolytic polymerization method are known. LB film is a method in which molecules containing parent wood groups and hydrophobic groups are spread on the surface of water and collected onto a substrate. I can't.

The electrolytic polymerization method is a method in which an organic substance is dissolved in an aqueous or organic solvent and electrolyzed to deposit a polymerized film on an electrode. Until now, organic materials have been limited to molecules with unsaturated bonds, and it has not been possible to form films of inorganic materials.

Recently, Saji et al. (J, Am, Cj2emSoc, 109.
5881 (1987).

Chem, Leff 893 (1988)) reported a method for electrolyzing micelles.

We have already found that it is possible to form films of other water-insoluble organic particles and water-insoluble inorganic particles using this micelle electrolysis method.

These micelle electrolysis methods involve dispersing or softening water-insoluble or poorly water-soluble organic or inorganic substances in surfactant micelles that have the characteristic of being charged by electrolysis, and then destroying the micelles by electrolysis. , organic substances, and inorganic substances are deposited on electrodes.

[Problems to be Solved by the Invention] Thin film formation by micelle electrolysis involves depositing fine particles in a solution (fine particles in micelles) on an electrode, and is an extremely low energy film forming method. For this reason, the fine particles dispersed in the solution simply adhere to the electrode, and the adhesion is very weak, causing the film-formed part to peel off even when the electrode is pulled out of the micelle solution. There was a problem.

Furthermore, when the film peels off, there are cases where only the upper layer of the film peels off, which poses a problem in the smoothness of the formed micelle film.

If the micelle membrane is not smooth, there will be restrictions on the fields of application. For example, when manufacturing a color filter for a liquid crystal panel using this film, if the film has large irregularities, problems such as poor alignment are likely to occur, making it impossible to apply stress as a color filter.

An object of the present invention is to obtain a uniform film with excellent smoothness by increasing the adhesion of this film forming part.

[Means for Solving the Problem 1] A non-aqueous or poorly water-soluble organic or inorganic substance is dispersed into a colloid in a micelle solution of a surfactant that has the property of being charged by electrolysis, and a supporting electrolyte and a cation are added to the micelle solution. Electrolysis is carried out on the formed dye pigment film in a solution of a liquid electrodeposition solution, as the first electrolysis at a temperature above the micelle breakdown potential and below the electrodeposition potential, and as a second electrolysis, electrolysis is carried out at a potential above the electrodeposition potential. This method is characterized by forming a film of fine particles of an organic or inorganic substance that is insoluble or poorly soluble in water.

Next, each process will be explained in order.

The micelle solution of the present invention contains at least a surfactant, a supporting electrolyte, a water-insoluble or poorly water-soluble organic or inorganic substance, and components of an electrodeposition solution.

Any surfactant may be used as long as it can destroy the micelles of the surfactant by electrolytic oxidation.
For example, a metallocene group [M
(ci Hs) 2: M=T 1, V+, Cr
, Fe, Co, Ni, Ru, Os.

Such surfactants include Pd, etc.].

One or more of these surfactants are dissolved in an aqueous solution to form micelles, into which water-insoluble or poorly water-soluble organic or inorganic substances are dispersed or suspended.

The surfactant concentration may be at least the micelle concentration, and the upper limit is not limited.

There are no limitations on the supporting electrolyte, and I
It is sufficient if the concentration is within a range where the R drop can be ignored.

As a component of the electrodeposition liquid, it has a carboxyl group,
A resin prepolymer neutralized with ammonia or an organic amine, etc. coexists with a water-soluble melamine resin, phenol resin, etc. as a crosslinking agent.

A test electrode, a counter electrode, and a reference electrode are immersed in a micelle solution having the above composition, and a potential of more than the micelle breakdown potential and less than the prepolymer electrodeposition potential is applied to the test electrode. After forming a film, 1
By applying a potential higher than the i@ potential for a short time, a polymer was formed between the fine particles of the organic or inorganic film.

By repeating this process, it was possible to form a smooth, highly adhesive film made of organic or inorganic fine particles on the electrode.

Note that this film forming method is fundamentally different from a method in which a pigment or the like is dispersed in an electrodeposition solution to co-deposit the electrodeposition polymer and the pigment or the like in the ratio of the electrodeposition polymer to the pigment or the like. That is, the present invention is different in that the organic or inorganic fine particles ensure the adhesion of the film by allowing the 1i-adhered polymer to "infiltrate" the gaps, so to speak.

Therefore, if the amount of pigment, etc. per unit area is constant, the film thickness of the present invention is always thinner than that of an electrodeposited film.

This will be explained in detail below using examples.

[Example] ITO was formed as a transparent electrode on a glass substrate with a diagonal size of 5 inches by sputtering, and was further formed as a striped electrode of 300 stripes with a width of 100 μm using a photolithography method.

Next, red, green, and blue pigments (organic pigments) with the composition shown in Table 1.
A micellar colloid aqueous solution was prepared.

Table 1 * l * 2 * 3 * 4 Ferrocenyl PEG (manufactured by Dokuchikagaku) (can be oxidized and reduced by electrolysis) Lithium bromide anthraquinone-based door brominated chlorinated copper phthalocyanine *5 α-type copper phthalocyanine In addition, these 3 A 7:3 mixture of acrylic acid and melamine was added to a 7:3 micellar colloid solution.
．． It was added so that it contained 5wt%.

During electrolysis, the electrodes were selectively energized so that the dye thin film formed a repeating striped pattern of blue, green, and red. During this electrolysis, first the electrolytic potential was set to 0.4 V (us,
S, C, E, ), and the electrolysis time is 0,
The thickness was adjusted to 3 μm. Next, the electrolytic potential is 2,
As OV (us, S, C, E,), Bommer is 0
．． Electrolysis was carried out only for the time required to "seep into" the 3 μm gap in the pigment film. By repeating this three times, each pigment film becomes 1
A color filter with a stripe pattern of 0 μm was obtained. That is, the film thickness increased by only 0.1 μm due to electrodeposition.

Thereafter, a color filter with good adhesion was obtained by baking at 180° C. for 30 minutes.

That is, even when the completed color filter was subjected to a peel test using Scotch tape, the dye film did not peel off at all.

Furthermore, the color filter surface was extremely smooth, and there was no problem of the dye film peeling off in the micellar colloid solution.

This color filter was passed through the liquid crystal panel process to form a panel, but there were no problems with the adhesion of the film, and there was no damage caused by the rubbing process.

Using this panel, we investigated the driving characteristics of the liquid crystal, but no differences were observed compared to the case of a conventional dye thin film alone. Furthermore, durability and reliability under an environment of 60°C x 90% were evaluated, and no problems such as poor orientation occurred.

[Effects of the Invention] As can be seen from the Examples above, when the present invention was used, it was possible to improve the adhesion of a film formed by micelle electrolysis, and to obtain a flat film.

As a result, when the present invention was applied to a color filter for a liquid crystal panel, for example, there was no difference compared to the case of a conventional dye film alone, and no problems such as poor alignment occurred.

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Claims (1)

[Claims] 1. A non-aqueous or poorly water-soluble organic or inorganic substance is dispersed and colloided in a micelle solution of a surfactant that has the property of being charged by electrolysis, and a supporting electrolyte and electrodeposited in the micelle solution. In the dissolved solution, electrolysis is performed on the formed dye pigment film as a first electrolysis at a voltage higher than the micelle breakdown potential and lower than the electrodeposition potential, and as a second electrolysis, electrolysis is performed at a voltage higher than the electrodeposition potential. A thin film deposition method using micelle electrolysis, which is characterized by depositing a film of fine particles of an organic or inorganic substance that is poorly soluble in water or water. 2. The micelle electrolysis according to claim 1, wherein the first electrolysis and the second electrolysis are repeated two or more times to form a film of fine particles of an organic or inorganic substance that is insoluble or poorly soluble in water. Thin film deposition method by method.