JPH0579756B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a multi-stage thin film forming method, and more specifically, a hydrophobic substance is solubilized using a micelle agent, and an electrochemical method is used to solubilize a hydrophobic substance to form an optical material such as a color filter. The present invention relates to a multi-stage film forming method that can easily and efficiently produce an electrode having a thin film made of a plurality of types of hydrophobic substances that can be used as photosensitive materials, electronic materials, etc. [Prior Art] Known methods for producing color filters include dyeing methods, printing methods, color resist methods, polymer electrodeposition methods, and micellar electrolysis methods. Among these, micellar electrolysis is a film-forming method that has recently attracted attention, and refers to a method in which a micellar agent of a hydrophobic substance such as a dye is electrolytically treated to form a thin film on the electrode surface (Japanese Patent Application Laid-Open No. 63−
(See Publication No. 243298). This method has the feature that it is possible to form a thin film in an aqueous system, and the obtained thin film has conductivity in an aqueous solution.
It is expected to develop as a method for forming thin films. However, by applying this thin film formation method to color filters, three colors of RGB (R: red, G: green, B: blue), etc. are formed on multiple electrodes such as ITO electrodes patterned on an insulating substrate. In the case where thin films of multiple colors are continuously formed, complicated special wiring such as three-dimensional wiring as shown in FIG. 2 is required. FIG. 2 is an explanatory plan view showing three-dimensional wiring in the case of forming three-color dye films of R, G, and B on an insulating substrate with ITO electrodes, in which the wirings to each electrode cross each other. At this intersection, SiO ₂ , Al ₂ O ₃
Since it is necessary to coat each wiring with an insulating film such as, manufacturing is not easy. [Problems to be Solved by the Invention] The present invention has been made based on the above-mentioned circumstances, and its purpose is to easily and efficiently solve multiple hydrophobic It is an object of the present invention to provide a multi-stage thin film forming method capable of forming a film of a substance. [Means for Solving the Problem] As a result of intensive research to solve the above problem, the present inventors focused on the fact that the thin film formed has conductivity, and formed a thin film on an electrode. After that,
It has been found that the above object can be achieved by removing unnecessary electrode lead-out parts together with the thin film by electrolytic etching, and then by not interfering with the selective connection between the electrode lead-out parts that form the thin film and the lead-out electrodes. Based on this knowledge, we have completed the present invention. That is, the present invention provides a method for applying a plurality of hydrophobic substances by micelle electrolysis to the surface of a plurality of electrodes that are patterned on an insulating substrate into a shape having a plurality of sets of take-out portions with different take-out positions for each set. When forming a thin film, the extraction part of one set of electrodes is connected to the extraction electrode, a thin film of a hydrophobic substance is formed on the electrode by micelle electrolysis, and then the extraction part of the other set of electrodes is connected to the extraction electrode. In order to prevent a short circuit when the electrodes are connected, the lead-out part of the set of electrodes on which a thin film has been formed is selectively removed by electrolytic etching, and then the lead-out part of the other set of electrodes is connected to the lead-out electrode. A thin film of another hydrophobic substance is formed on another set of electrodes by a micelle electrolysis method, and by continuing this operation a necessary number of times, a plurality of thin films of a hydrophobic substance are formed on the plurality of sets of electrodes. The present invention provides a multi-stage film forming method for thin films. In the method of the present invention, the micelle electrolysis method refers to adding a micellar agent made of a ferrocene derivative and a hydrophobic substance to an aqueous medium whose electrical conductivity has been adjusted by adding a supporting electrolyte as necessary to water and thoroughly mixing the mixture. This is a method in which a micelle solution containing a hydrophobic substance is created by stirring and dispersing it inside the micelles, and by electrolyzing this, particles of the hydrophobic substance are deposited on the anode to form a thin film. In the micelle electrolysis method, the micelles are attracted to the anode by electrolytic treatment, and the ferrocene derivatives in the micelles lose electrons on the anode, and the micelles collapse and the hydrophobic substances inside are deposited on the anode. On the other hand, the oxidized ferrocene derivative is attracted to the cathode, receives electrons, forms micelles again, and takes the hydrophobic substance inside. In the process of repeating the formation and collapse of micelles, particles of the hydrophobic substance are deposited on the anode to form a thin film. By further subjecting the thin film thus formed to a heat treatment, a stable thin film that is not redissolved in the micelle solution can be obtained. The present invention uses the above-mentioned micelle electrolysis method to simply and efficiently provide a plurality of sets of thin films of a hydrophobic substance on a plurality of sets of electrodes.The present invention will be described in detail below based on the drawings. FIG. 1 shows a substrate consisting of ITO electrodes provided on an insulating substrate 1, in which five sets of ITO electrodes A to E are patterned with their extraction portions slightly shifted. When these five sets of electrodes are provided with five sets of thin films of hydrophobic substances, the central part 3 of the figure becomes the effective part of the electrodes on which the thin films are formed. In the figure, the electrodes are provided linearly and in parallel in this effective part, but they may also include dots or diagonal wiring. To explain the film forming procedure, first, as shown in FIG.
A take-out electrode 5 made of platinum wire, conductive rubber, silver paste, etc. is connected. When this substrate is immersed on the left side of the electrode A in a micelle solution 6 in which a hydrophobic substance a such as a dye is solubilized and subjected to electrolytic treatment using the micelle electrolysis method, a thin film is formed only on the shaded area of the electrode A. . Next, the substrate is turned upside down and the right side of the electrode A is immersed in the etching solution 7, as shown in Fig. 4, and the taken out electrode 5 is connected to the left taken out part of the electrode A formed by the etching process. When etching is performed, the portion of electrode A immersed in the etching solution is removed together with the thin film. As a result, the connection between the next extraction part of electrode B and the extraction electrode is changed to electrode A.
This can be done extremely easily without fear of short-circuiting. Next, as shown in Fig. 5, the top and bottom of the substrate are returned to their original positions, the left side of electrode B is immersed in micellar solution 8 in which hydrophobic substance b has been solubilized, and the taken-out part of electrode B is connected to the taken-out electrode. When electrolytic treatment is performed using the micelle electrolysis method, a thin film is formed only on the shaded area of electrode B in the figure. Next, the etching solution immersed part of electrode B is removed in the same manner as in , to facilitate connection between the next extraction part of electrode C and the extraction electrode. By repeating the above operations as necessary,
It becomes possible to continuously form thin films of multiple hydrophobic substances. Therefore, the multi-stage film forming method of the present invention is an extremely effective film forming method for manufacturing color filters that require the formation of thin films of three colors of dyes on electrodes. In the above explanation, the multi-stage film forming method of the present invention has been explained in the case where micellar electrolysis and electrolytic etching are applied alternately to the substrate shown in FIG. Thereafter, electrolytic etching may be performed to remove unnecessary film-formed electrode portions. The micellizing agent used in the micelle electrolysis method is made of a ferrocene derivative. There are various types of ferrocene derivatives, and examples include the following three types (1), (2), and (3). First, (1) a ferrocene compound (ferrocene or an alkyl compound suitable for ferrocene) is added to an ammonium type (preferably quaternary ammonium type) cationic surfactant having a main chain of 4 to 16 carbon atoms (preferably 8 to 14 carbon atoms). or a substituent such as an acetyl group). Here, if the number of carbon atoms in the main chain is small, micelles will not be formed, and if the number of carbon atoms is too large, it will not dissolve in water. There are various ways in which the ferrocene compound is bonded to the surfactant, and can be roughly divided into those bonded to the end of the main chain of the surfactant, those bonded directly or through an alkyl group in the middle of the main chain, and those bonded within the main chain. Examples include those incorporated into. Such ammonium type ferrocene derivatives have the general formula

[Formula] (In the formula, R ¹ and R ² each represent hydrogen or an alkyl group having 1 to 4 carbon atoms (however, not exceeding the integer m described below), and Z ¹ and Z ² each represent hydrogen or a substituent (methyl group, ethyl group, methoxy group, or carbomethoxy group), and X represents a halogen. Also, m and n are m≧0, n≧0, and 4≦m
Indicates an integer satisfying +n≦16. ), general formula

[Formula, R ¹ , R ² , X, Z ¹ and Z ² are the same as above (however, the number of carbon atoms in R ¹ and R ² does not exceed the integer h described later). , j and k are h≧0, j
≧0, k≧1, and represents an integer satisfying 3≦h+j+k≦15, and p represents an integer satisfying 0≦p≦k−1. ),

[Formula, R ¹ , R ² , X, Z ¹ and Z ² are the same as above (however, the number of carbon atoms in R ¹ and R ² does not exceed the integer r described later). , s and t are r≧
0, s≧0t≧1, and 4≦r+s+t≦16
Indicates an integer that satisfies ), or

Examples include those represented by the formula: (wherein R ¹ , R ² , X, Z ¹ , Z ² , r, s, and t are the same as above). Specific examples of ferrocene derivatives as micellizing agents include:

【formula】

【formula】

[Formula] etc. (2) Other types of ferrocene derivatives include:

Examples include ether-type ferrocene derivatives represented by Here, a represents an integer of 2 to 18, and b is a real number of 2.0 to 50.0. a is 2 as mentioned above
Since it is an integer of ~18, an alkylene group having 2 to 18 carbon atoms, such as an ethylene group or a propylene group, is interposed between the ring member carbon atom and Y. Furthermore, the alkylene group may be branched or contain a phenyl group. Alternatively, hydrogen in an alkylene group may be substituted with a halogen atom, a methyl group, or a methoxy group. Also, b is
It means not only an integer between 2.0 and 50.0 but also a real number including these, which indicates the average number of repeating oxyethylene groups (-CH ₂ CH ₂ O-) constituting the ferrocene derivative. Furthermore, Y in the above general formula is oxygen (-O-), oxycarbonyl group (-O-CO-), or

【formula】

[Formula] is shown, and Z ¹ and Z ² each represent hydrogen or a substituent as described above. Furthermore, (3) other types of ferrocene derivatives include:

〔Example〕

Hereinafter, the present invention will be explained in detail based on Examples, but the present invention is not limited thereto. Example 1 As a nonionic micelle agent in 100c.c. of water

〔Effect of the invention〕

According to the method of the present invention, films of a plurality of hydrophobic substances can be easily and efficiently formed without special wiring such as three-dimensional wiring. In particular, it can be suitably used in the production of color filters that require the formation of thin films of RGB three-color pigments.

[Brief explanation of drawings]

FIG. 1 is a plan view of an insulator substrate with electrodes to which the multi-stage film forming method of the present invention is applied. FIG. 2 is an explanatory diagram illustrating a conventional multi-stage film forming method. 3 to 6 are explanatory diagrams for explaining the multistage film forming method of the present invention. FIG. 7 is a plan view of an insulator substrate with electrodes to which the multi-stage film forming method of the present invention is applied. 8 to 11 are explanatory diagrams for explaining an embodiment of the multi-stage film forming method of the present invention. Explanation of symbols, 1... Micelle solution, 2... Electrode, 3...
Effective electrode part, 5... Takeout electrode, 6, 8, 9, 1
0, 12... Micellar electrolyte, 7, 11... Etching solution.

Claims (1)

[Claims] 1. When forming multiple thin films of hydrophobic substances by micelle electrolysis on the surface of multiple electrodes that are patterned on an insulating substrate in a shape that has multiple sets of extraction parts with different extraction positions for each group. To,
When the extraction part of one set of electrodes and the extraction electrode are connected, a thin film of a hydrophobic substance is formed on the electrode by micelle electrolysis, and then the extraction part of another set of electrodes is connected to the extraction electrode. To prevent short circuits, the lead-out portions of the set of electrodes on which a thin film was formed were selectively removed by electrolytic etching.
Next, connect the take-out part of the other set of electrodes to the take-out electrode, form a thin film of another hydrophobic substance on the other set of electrodes by micelle electrolysis, and repeat this operation a necessary number of times to form multiple sets of electrodes. A multi-stage thin film forming method characterized by forming thin films of multiple hydrophobic substances on an electrode.