JPS60184841A - Manufacture of multi-color surface colored body - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

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 for producing multicolor surface blue bodies include methods such as screen printing and photolithography. However, with screen printing, there is no need for resist dyeing to prevent the already colored areas from being dyed twice in the next dyeing process, but there is a limit to the miniaturization of the pattern, and as the number of colors increases, the printing position increases. The accuracy of becomes worse.

Although photolithography is possible for fine patterns,
It is necessary to carry out one photolithography step t for each color change, and a resist dyeing method is required to prevent double dyeing, making the process extremely complicated.

Therefore, in Japanese Patent Application No. 57-235954, the present inventor developed a multicolor pattern that does not shift even when the pattern becomes fine, allows color changes without special resist dyeing, and is robust.
We proposed a simple manufacturing method. In this method, a conductive film is placed on a substrate as an electrode, and a colored layer is selectively formed using a solution consisting of a polymer and a dye.One voltage is simultaneously applied to the electrodes to be electrodeposited in the same color. However, 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 short-circuiting a part of the conductive layer within the substrate in advance, it is possible to use multiple colors more easily and without worrying about poor contact. It is designed so that it can be changed. As long as the substrate used in this method has an insulating surface, there are no restrictions on its material or shape, 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 M-coating a polymer, which is an important point of the present invention, will be described. High molecular? One method for electrodepositing 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. A12・196B). Recently, research has also been actively conducted in which conductive polymers such as polypyrrole and polythenylene are produced on electrodes by completely electrochemically polymerizing virol and thiophene. However, such a method of directly electrochemically polymerizing a monomer is not suitable for use in the present invention, such as the efficiency is still not good, and the obtained film is already colored, so the coloring is not arbitrary. has problems. Another method for electrodepositing a polymer on an electrode is to completely insolubilize and precipitate the polymer on the electrode from a polymer solution. As an example of this, a method called electrocoating is known industrially, in which a pigment is dispersed in an aqueous polymer solution, the entire metal is immersed, and used as an electrode, and a colored layer is electrodeposited on the metal. Used for body pre-coating, etc. The principle of this method is that hydrophilic groups and
For example, a carboxyl group is introduced, and the carboxyl group is neutralized with an inorganic alkali, an organic amine, etc. to make it water-soluble.

Then, when the electrode is completely 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 precipitation of polymer is observed.

2H,0-4n"+Ot↑+4e In addition, if a basic group (for example, polyamine) is used as the hydrophilic group and it is made water-solubilized by acid, polymer precipitation will be observed on the cathode. Become.

If the electrodeposited polymer is electrically insulating, the current decreases as the electrode is coated with the polymer, and further coating can be prevented, so an increase in film thickness cannot be expected. Complete coverage at the initial stage is avoided due to oxygen bubbles generated by decomposition, and a certain degree of film thickness can be obtained by the time it becomes an insulating layer. Usually 100 to 2 with electrodeposition coating
A film thickness of 10 to 20 μm was obtained by applying a voltage of 0.0 V, but if the goal is to produce a multicolored surface colored object with high precision and fineness, the distance between patterns will be several μm, and if the film thickness is thick, Fusion between patterns occurs. Therefore, the colored layer should be thinner, and preferably about 1 μm thick. For this purpose, as will be described later in Examples, it is necessary to set the resin concentration, voltage, and solvent composition to be all optimal. The polymer layer thus obtained has low water content due to the effect of electroosmosis, resulting in a uniform film with better adhesion than a film produced by a coating method or the like.

Polymers for anion 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. Copolymers of and their esters are used, and depending on the characteristics of the electrodeposited film, other polymers or organic compounds with functional groups may be introduced into the polymer skeleton. transparency,
Acrylic or polyester polymers are suitable when all aspects of appearance, such as gloss, are important. 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 electrodeposition layer will not be sufficiently insolubilized, resulting in an uneven film, and if there are too few, it will be difficult to neutralize. water solubility becomes insufficient. Water is the main component of the polymer solvent, and isoprohanol + n-phthyl alcohol, t-phyl alcohol, methyl cellosolve, ethyl cellosolve, inglovir cellosolve, butyl cellosolve.

Hydrophilic solvents such as diethine glycol methyl ether, diethylene glycol ethyl ether, and diacetone alcohol are included as polymerization solvents. The type and amount of the hydrophilic solvent contained greatly influences the film thickness and uniformity of the electrodeposited layer.

Coloring is possible by electrodeposition with dyes or pigmented polymers.

Unfortunately, the hardened colored layer has become a complete P3 edge layer.
Re-electrodeposition or double dyeing will not occur even if the electrodeposition bath is immersed in the electrodeposition bath and energized twice. Therefore, when electrodepositing the second and subsequent colors of the present invention, the conductive layer that has already been electrodeposited other than the terminals of the conductive layer to be selected will not be redeposited or dyed twice. By partially twisting the conductive layer and simultaneously applying voltage to all the electrodes, it is possible to easily produce the entire body with a multicolored surface.

〔Example〕

Hereinafter, a method for producing a multicolored surface-colored body will be specifically described based on Examples.

(Example 1) As an example, a transparent multicolored surface-colored body with a stripe pattern having a total a width of 200 μm and color-coded in the order of red, green, and blue as shown in FIG. 1 was prepared.

The manufacturing method will be specifically described below.

■ In the buttering process 1, a transparent substrate made of glass is used, and vcOV is applied on the transparent substrate.
A tin oxide transparent conductive film is formed by method D. By the transparent conductive Bkk etching, the first color conductive 11Q is patterned into a stripe shape short-circuited at the edge of the substrate.
1jJ! Obtain j 2 , 2', 2''.

■ Electrodeposition process Next, paint with the following composition (Nisvia ED-3000 manufactured by Shinto Paint) Nisvia BD-! +000 Make an electrodeposition bath with the following composition.

The dye used is limited to one that is soluble in methyl cellosolve, which is a hydrophilic solvent, and the upper limit of the dye weight ratio X is determined by its solubility. In other words, in order to obtain a high coloring density, it is necessary to have a large l"tx and a high solubility of the dye in methyl cellosolve. Desirable dyes are oil-soluble dyes with a metal complex structure of gold that is soluble in hydrophilic solvents. This dye has high solubility in hydrophilic solvents and has excellent light resistance (product name is ij Aizen S7).
1lon 01eosolFast,, Neozap
on Valifast et al.). For example, some molecules have the following molecular structure:

The procedure for making the color index number 5 solvent Red bath is to dissolve Nisbia KD-'5000-(H) in water.Next, methyl cellosolve in which the dye has been dissolved is added to the aqueous solution to uniformly disperse the dye.At this time, methyl cellosolve is It works as a dispersion medium, but if the amount added or the number of carbon atoms in the alkyl group of cellosolve increases,
This results in an increase in film thickness and non-uniformity of the film.

In the electrolayer bath prepared as above, the transparent electrode 2゜21
．． 2" is formed on the transparent substrate 1. Of the transparent molds 1i 2 , 2/, 2" that have been turned,
First, a voltage of 10 to 40 V is applied between the transparent electrode 2 to be dyed in the first color as an anode and a counter electrode for 6 minutes.

Since the transparent electrodeposition 2 is patterned in advance so as to be electrically short-circuited, is it a conductive comb, etc.? It can be powered without using it. At this time, a large current flows immediately after the current is turned on, but it gradually decreases and approaches zero.

After energizing, pull up the transparent substrate 1 and wash it thoroughly with water! Wash away the molten fL adhering to areas where no pressure is applied. After washing with water and drying, a highly transparent colored layer is formed on the electrode to which a voltage is applied.

■ Curing process Next, the polyester resin and melamine resin in the colored layer formed by electrodeposition are baked! , and harden by performing a polycondensation reaction. Baking is performed in air at 175° C. for 30 minutes to cure the color; if you want to increase the fastness of the colored layer, baking can be done for a longer time or by reducing the pressure. The thickness of the colored layer after curing was 1.5 μm.

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 two-color dyeing will occur. Even if all the electrodes on which all the colored layers have already been formed are selected at the same time and a voltage is applied, the second or subsequent colored layers can be formed only in the necessary areas. That is, selective electrodeposition can be performed by contacting a conductive rubber or the like with the TDa part for the second time and the b part for the second time.

In this way, by repeating the steps of electrodeposition and curing in direct deposition baths of different tones, a multicolored surface-colored body can be realized.

In this embodiment, a red colored layer 6, a green colored layer 3', and an evening colored layer 3 are formed on the transparent electrodes 2, 2', and 2'', respectively. It was manufactured using the following method: electrodeposition process - curing process - electrodeposition process - curing process, and could be carried out very easily. According to this method, if the desired precision is achieved in the first buttering process,
There is no accuracy deterioration in the post-process, and in this example also the transparent electrodes 2, 2', 2# and the colored layers 3, 3', 3
There was no pattern shift or protrusion between '.

In addition, in this embodiment, the transparent electrode 2 has 2' and 2'.
During the electrodeposition of #2, the transparent electrode 2' was selected and a voltage was applied at the same time as the #2 electrodeposition, but no increase in film thickness due to re-electrodeposition or change in color due to coloring with other colors was observed. Furthermore, the colored layer obtained was uniform, resistant to attack by acids, alkalis, various organic solvents, hot water, etc., and had sufficient strength against peeling.

The metal complex dye used is extremely stable in the colored layer, with a value of 95% or more of the initial light absorption rate even after 560 hours of carbon arc testing. It had excellent light resistance.

Examples of applications of the multicolored surface-colored body as shown in this example are that it is useful as a means for adding multiple colors to display elements such as liquid crystal displays used in calculators, watches, etc.; It can be used as an electrode and has extremely high utility value, almost like a matrix drive element.
This is Lee Ujin II. In addition, when used for display elements,
A short circuit in the conductive film poses a problem, but it can be easily solved by cutting off the short circuit after producing the filter.

(Example 2) As shown in FIG. 2, the transparent electrode 2' to be electrodeposited for the second time was also buttered so that it was short-circuited on the side opposite to the transparent electrode 2. The same effect as in Example 1 was obtained when conductive rubber was electrodeposited on the part (a) in FIG. 2 only during the third energization in the bath of Example 1. In this example, since the conductive rubber was only used once, it was possible to achieve multiple colors more easily.

(Example 6) As shown in FIG. 3, as in Example 2, transparent electrodes 2, 2
' was short-circuited and short-circuited on the back side of the substrate via the voltage application terminal 2# hasle hole. When the electrodeposition and curing were repeated using the same bath as in Example 1, the same effects as in Example 1 were obtained. Further, in Examples 1 and 2, since the conductive rubber was used in all phases, there were cases where parts were not electrodeposited due to poor contact, but this was not observed at all in this example. Furthermore, energization during electrodeposition could be carried out more easily. Although the process 8 of forming the transparent lightning wL on the substrate is somewhat complicated, it is advantageous in these respects.

〔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 polychromatic surface colored body has high precision, high fineness, robustness, and high reliability, and can be applied not only to multicolor means for display elements and optical multicolor separation means for image pickup tubes, etc. , and is expected to be applied in many fields.

[Brief explanation of the drawing]

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 or more Applicant: Seiko Electronic Industries Co., Ltd. (1 other person) Agent
Patent Attorney Mogami Tsutomu No. 10 Figure 2, page 1 continued ■ Inventor Mitsuru Suginoya 0 Inventor Yutaka Sano [Secretary] Inventor Kato Naomizo @ Inventor Nomura Minister of Agriculture @ Inventor En 1) Soma 0 Invention Shinji Ito 6-31-1 Kameido, Koto-ku, Tokyo Seiko Electronics Industries Co., Ltd. 6-31-1 Kameido, Koto-ku, Tokyo Seiko Electronics Industries Co., Ltd. 6-31-1 Kameido, Koto-ku, Tokyo Seiko Electronics Industries Co., Ltd. 3-1-7 Tsuchiyamanone, Zushi 2-1 Higashi-Narashino Minami, Chigasaki City 5-1-1 Higashi-Narashino, Narashino City 6-6-14 Kanamachi, Katsushika-ku, Tokyo 3-7-24 Higashi-Narashino, Narashino City

Claims (3)

[Claims] (1) A multi-color method in which conductive layers with a specific pattern are formed on a substrate and are insulated from each other, and then colored layers are sequentially formed by electrodeposition of polymers and dyes on these conductive layers. In a method for manufacturing a surface-colored body, at least two or more voltage application terminals of at least one color of a conductive layer to be colored in the same color are electrically short-circuited in the substrate and energized to form a colored layer by electrodeposition. A method for producing a multicolored surface-colored body, which is characterized by: (2) At least two voltage application terminals of at least one color of the conductive layer electrodeposited in the same color, with all voltage application terminals of a plurality of conductive layers arranged on the substrate having different lengths for each color. 2. A method for manufacturing a multicolored surface-colored body according to claim 1, characterized in that the above components are electrically short-circuited within the substrate in advance. (3) The voltage application terminals of the plurality of conductive layers arranged on the substrate are electrically short-circuited via through holes (7) at the back side of the substrate (1). A method for producing a multicolored surface-colored body as described in Section 1.