JPH0434638B2 - - Google Patents

Description

[Detailed description of the invention]

[Field of the Invention] The present invention relates to a simple method for producing a multicolored surface-colored body. [Prior Art] Generally, methods such as screen printing and photolithography are used to produce a multicolored surface blue body. However, with screen printing, there is no need for resist dyeing to prevent already colored areas from being dyed twice in the next dyeing process, but there is a limit to the miniaturization of patterns, and the more colors there are, the more printing Position accuracy deteriorates. Although photolithography allows for fine patterns,
It is necessary to go through a photolithography process every time the color is changed, and a resist dyeing method is required to prevent double dyeing, making the process extremely complicated. Therefore, the present inventor proposed in Japanese Patent Application No. 57-233934 (Japanese Unexamined Patent Publication No. 59-115886) that it is possible to change the color without any special resist dyeing without causing any deviation even if the pattern becomes fine. We proposed a method to easily produce robust multicolor patterns. In this method, a conductive film is placed on a substrate as an electrode, and a colored layer is selectively formed from a solution consisting of a polymer and a dye.A voltage is simultaneously applied to the electrodes that are electrodeposited in the same color. In this case, there is a problem in that it is difficult to take out the electrodes. [Purpose of the Invention] The present invention has been made to eliminate the above-mentioned drawbacks, and by electrically shorting a part of the conductive layer in the substrate in advance, it is easier to prevent poor contact. This allows for multi-coloring without worry. As long as the surface of the substrate used in this method is insulating, the material and shape of the substrate are not limited as long as a conductive thin film layer with good adhesion to the substrate is selected. [Structure of the Invention] Hereinafter, a method for forming a colored layer by electrodeposition of a polymer, which is an important point of the present invention, will be described. One method for electrodepositing a polymer on an electrode is to electrochemically polymerize a monomer on the electrode. As an example of this method, there is a report that a polymer film was obtained by electrochemically polymerizing various vinyl compounds on an iron plate (Metal Surface Technology Vol. 19, No. 12, 1968).
Recently, research has also been actively conducted in which conductive polymers such as polypyrrole and polythienylene are formed on electrodes by electrochemically polymerizing pyrrole, thiophene, etc. However, such direct electrochemical polymerization of monomers is not yet efficient, and the resulting film is already colored.
It has problems when used in the present invention, such as lack of arbitrariness in coloring. Another method for electrodepositing a polymer on an electrode is to insolubilize and precipitate the polymer on the electrode from a polymer solution. One example of this is an industrially known method called electrocoating, in which a pigment is dispersed in an aqueous polymer solution, a metal is immersed, and used as an electrode, and a colored layer is electrodeposited on the metal. It is used for pre-coating, etc. The principle of this method is to introduce a hydrophilic group, such as a carboxyl group, into a polymer, and then neutralize the carboxyl group with an inorganic alkali, organic amine, etc. to make it water-soluble. Then, when the electrode is immersed in an aqueous solution of the water-soluble polymer and a voltage is applied, the carboxyl anions isolated in the aqueous solution electrophores toward the anode and react with protons generated by water electrolysis on the electrode. As a result, the polymer becomes insolubilized and precipitates out. That is, the reaction shown in the following formula occurs on the anode, and polymer precipitation is observed. Furthermore, if a basic group (for example, polyamine) is used as the hydrophilic group and is neutralized and water-solubilized with an acid, precipitation of the polymer will be observed on the cathode. If the electrodeposited polymer is electrically insulating, the current decreases as the electrode is coated with the polymer, preventing further coating, so an increase in film thickness cannot be expected; however, in reality, the electricity of water Initial complete coverage is avoided due to enzyme bubbles generated by decomposition;
A certain amount of film thickness can be obtained before it becomes an insulating layer. Normally, in electrodeposition coating, a film thickness of 10 to 20 μm is obtained by applying a voltage of 100 to 200 V, but with high precision,
When a highly fine multicolored surface colored body is intended, the distance between the patterns is several μm, and if the film thickness is thick, fusion between the patterns occurs. Therefore, the colored layer should be thinner, preferably about 1 μm. For this purpose, it is necessary to optimally set the resin concentration, voltage, and solvent composition, as will be described later in Examples. The polymer film obtained in this manner has a low water content due to the effect of electroosmosis, and is a uniform film with better adhesion than a film produced by a coating method or the like. Examples of polymers for anionic electrodeposition include adducts of natural drying oil and maleic acid, alkyd resins with carboxyl groups introduced, adducts of epoxy resins with maleic acid, polybutadiene resins with carboxyl groups, acrylic acid or methacrylic acid, etc. Copolymers with esters thereof are used, and other polymers or organic compounds having functional groups may be introduced into the polymer skeleton depending on the characteristics of the electrodeposited film. transparency,
If appearance such as gloss is important, acrylic or polyester polymers are suitable. In addition, the amount of hydrophilic functional groups such as carboxyl groups and hydroxyl groups in the polymer is important; if there are too many hydrophilic groups, the electrodeposited layer will not be sufficiently insolubilized, resulting in an uneven film.
If the amount is too small, water solubility during neutralization will be insufficient. Water is the main component of the polymer solvent, but isopropanol, n-butyl alcohol, t-butyl alcohol, methyl cellosolve, ethyl cellosolve, isopropyl cellosolve, butyl cellosolve, diethine glycol methyl ether, diethylene glycol ethyl ether, diacetone alcohol Hydrophilic solvents such as the following are included as solvents for polymerization of polymers. The type and amount of the hydrophilic solvent contained greatly influences the film thickness and uniformity of the electrodeposited layer. Coloring is possible by electrodepositing dyes or pigments together with polymers. In addition, the cured colored layer is a complete insulating layer, and even if it is immersed in an electrodeposition bath again and energized, no redeposition or double dyeing will occur, so the second and subsequent colors of the present invention can be electrodeposited. In addition to the terminals of the conductive layer to be selected, a voltage is simultaneously applied to some or all of the electrodes of the conductive layer that have already been electrodeposited, thereby making it possible to easily produce a multicolored surface-colored body. . [Example] Hereinafter, a method for manufacturing a multicolor surface-colored body will be specifically described based on Examples. Example 1 As an example, a transparent multicolored surface-colored body having a stripe pattern as shown in FIG. 1 with a line width of 200 μm and color-coded in the order of red, green, and blue was prepared. The manufacturing method will be specifically described below. Patterning Step 1 is a transparent substrate made of glass, and a tin oxide transparent conductive film is formed on the transparent substrate by CVD. The transparent conductive film is patterned by etching into a stripe shape in which the first color conductive film is short-circuited at the edge of the substrate to obtain transparent electrodes 2, 2', 2''. -3000 (manufactured by Shinto Paint) Esbia ED-3000 Water-soluble polyester resin Water-soluble melamine resin 70wt% Butyl cellosolve Ethyl cellosolve n-butanol 30wt% Create an electrodeposition bath with the following composition.

〔Effect of the invention〕

As described above in detail in the examples, according to the present invention, there is no need to worry about poor contact during electrodeposition, the terminal can be easily removed, and a multicolored surface-colored body can be manufactured easily. is possible. In addition, the obtained multicolor surface colored body has high precision, high fineness, robustness, and high reliability.
The present invention is expected to be applied not only to optical polychromatic separation means such as image pickup tubes, but also to a wide variety of other fields.

[Brief explanation of drawings]

1, 2, and 3 are plan views of electrode formation for a multicolor surface-colored body used in an embodiment of the present invention, and FIG. 4 is a sectional view of the multicolor surface-colored body according to the present invention. 1... Substrate, 2, 2', 2''... Electrode, 3, 3',
3″...Colored layer, 4...Through hole.

Claims (1)

[Claims] 1. A step of forming a plurality of conductive layers arranged insulated from each other on a substrate, and selectively applying electricity to a part of the plurality of conductive layers to electrodeposit a polymer and a dye. Therefore, in a method for producing a multicolored surface colored body, which comprises a coloring step of forming a colored layer by adhering it on the conductive layer, and in which the coloring step is sequentially repeated to form colored layers of different colors, A first coloring step in which a part of the conductive layer is selectively energized to form a colored layer on the part of the conductive layer, and another part of the conductive layer is selectively energized and the other part is colored. When forming a colored layer on a conductive layer,
a second coloring step of forming a colored layer by bringing a conductor for applying a voltage to the conductive layer into contact with the other part of the conductive layer and applying electricity; The method for applying electricity to the conductive layer includes connecting a conductor for applying a voltage to the conductive layer to a part of the colored layer formed by the coloring process before the second coloring process, and a part of the colored layer to be colored. A method for producing a multicolored surface-colored body, characterized in that the method is carried out by contacting some of the other conductive layers in parallel and applying electricity. 2. In the step of forming a plurality of conductive layers on the substrate, a voltage application terminal for energization electrically connected to the conductive layer and the voltage application terminal are formed so that the lengths thereof are different for each color. 2. The multi-function device according to claim 1, wherein the voltage application terminals for at least one of the colors are formed so as to be electrically connected on the substrate. A method for producing a colored body with a colored surface.