JPS60184837A - Manufacture of multi-color surface colored body having conductivity - 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 Industrial Application This invention relates to a multicolored surface-colored body, and is particularly applicable to fields that require high precision, high fineness, and multicolor, such as display elements and image pickup tubes. It provides a method for manufacturing color filters, multicolor scales for microscopes, etc. by a simpler means, and in particular, it provides a method for producing multicolor scales for color filters, microscopes, etc., and in particular, it provides a method for manufacturing multicolor scales with conductivity by electrodeposition. Concerning a method of manufacturing a body.

BACKGROUND OF THE INVENTION The most convenient means for producing multicolored surface-colored bodies is printing. However, printing methods have difficulty in positioning when printing in multiple colors, and high precision and fineness cannot be achieved. Therefore, at present, high-precision, high-definition color filters for image pickup tubes and the like use photolithography. However, although photolithography is a fully satisfactory method in terms of high precision and fineness, it is necessary to go through a photolithography process every time one color is produced.
The manufacturing process becomes extremely complex.

Therefore, the inventors of the present invention previously applied for patent application No. 57-233934.
In this issue, we developed a simple method that does not cause pattern shift even when the pattern becomes finer or finer, and there is no need to go through a special process every time the color is changed. We proposed manufacturing by electrodeposition method. According to this technique, a multicolored surface-colored body is manufactured by a method in which a colored layer is formed by electrodeposition using a conductive thin film on a substrate as an electrode and a polymer electrodeposition bath. It is an object of the present invention to provide a method that further improves the method for producing a multicolored surface-colored body using the polymer electrodeposition method described above.

When a multicolor surface-colored body is used in a low-voltage display such as a liquid crystal display, the color filter acts as an insulating film, thereby reducing the effective voltage of the display element. Therefore, it becomes necessary to make the filter a very thin layer or to increase the driving voltage. The present invention has solved this problem by imparting electrical conductivity to the colored layer of a multicolored surface-colored body used as a color filter. For this purpose, a conductive thin film on a substrate is used as an electrode, and a conductive colored layer is formed by electrodeposition from a polymer electrodeposition solution containing an electrodepositable polymer, a dye, and conductive ultrafine particles, and the surface is multicolored. The body is manufactured.

According to the method of the present invention, a conductive thin film is patterned in a desired manner by vapor deposition using a mask, sputtering, or etching, so that polymers, dyes, and conductive ultrafine particles are selected in conductive areas to which a voltage is applied. It is possible to form a colored layer having isoelectricity without deviation from the desired pattern position by electrodeposition. Furthermore, by repeating this operation, a colored layer will not be formed again on the part that has been electrodeposited once, so it is possible to easily create multiple colors. The substrate used in this method only needs to have an insulating surface, and as long as a conductive thin film layer with good adhesion to the substrate is selected, there are no restrictions on its material or shape.

Both anionic and cationic electrodepositable polymers can be used, but since cationic polymers are deposited on the cathode, it is possible to widely use the material of the conductive thin film layer that inherently forms a colored layer. Cationic polymers are preferable because they have characteristics such as high current efficiency, high current efficiency, and stable bath liquid.

DESCRIPTION OF THE PREFERRED EMBODIMENTS An example of a method for forming a colored layer having electrical conductivity by a polymer electrodeposition method, which is an important point of the present invention, will be described below.

In this method, first, as described above, a conductive thin film is patterned on a glass substrate as an insulating substrate. Hereinafter, this will be referred to as a transparent electrode pattern. Second, a polymer electrodeposition composition containing a dye and conductive ultrafine particles is prepared with a solid content of about 4 to 25%.
In a polymer electrodeposition bath diluted with pure water to give a weight percentage of
A counter electrode made of platinum, stainless steel, etc. and a glass substrate with the above-mentioned transparent electrode pattern are immersed in the liquid. Next, a DC voltage of about 5 to 300 V is applied between the transparent electrode pattern to be colored and the counter electrode, using the transparent electrode pattern as a cathode in the case of the cationic & tif method and as an anode in the case of the anionic electrodeposition method. By this application, electrodeposited A1 containing dye and conductive ultrafine particles
The 1i product migrates only onto the transparent electrode pattern to which a voltage is applied, deposits as a coating film, and colors the transparent electrode pattern.

To obtain the required film thickness, electrodeposition conditions such as voltage, electrodeposition time, and liquid temperature are adjusted. The normal dry film thickness is 5 microns or less. Electrodeposition time is usually 5 to 180 seconds, liquid temperature is 10 to 30℃
It is.

After the electrodeposition time has elapsed to reach the required film thickness, stop energizing.
The glass substrate is removed from the bath, the remaining bath liquid is thoroughly washed away with pure water, and the coating is heated to harden.

In this way, a conductive transparent electrode pattern colored in one color is produced. Third, when making a multicolor filter with three colors of red, green, and blue, repeat the second coloring process described above with the other two colors.
Repeat on the transparent electrode pattern that requires coloring. As described above, a multicolor filter having three colors of conductivity is produced by the polymer electrodeposition method.

This method does not require a photophosphorography process during coloring, and does not require resist dyeing treatment, so the process is simple, and the transparent electrode pattern and the colored layer match in principle, allowing for high definition. This method fully solves the drawbacks of photography and printing methods, such as the fact that transparent electrode patterns are colored.

Next, the polymer electrodeposition liquid used in the molecular electrodeposition method, which is an important point of the present invention, will be explained. This configuration includes (1) an anionic or cationic synthetic polymer resin as a reforming component of the m film, (11) conductive ultrafine particles that impart conductivity to the coating film, and (fil) the coating film. It is transparent and consists of pigments such as pigments or dyes that give color, and in addition, as bath components, it improves electrodeposition characteristics and bath liquid stability.
Organic solvents used to facilitate manufacturing (V)
Neutralizing agent for making synthetic polymer resin soluble in water, (V
D Contains various auxiliary agents to improve the coating surface, electrodeposition properties, bath stability, etc.

The configuration contents will be explained in detail below.

Synthetic polymer resins used as film-forming components of coating films include anionic synthetic polymer resins such as acrylic resin, polyester Jfit, maleated oil, polybutadiene resin, and epoxy resin, and these resins may be used alone or in combination. In addition, examples of cationic synthetic polymer resins used in combination with crosslinkable resins such as melamine resins, phenol resins, and urethane resins include acrylic resins, epoxy resins, urethane resins, polybutadiene resins, and polyamide resins. These may be used alone or in mixtures, or in combination with crosslinkable resins such as urethane resins and polyester resins.

Acrylic resin, polyester resin alone or in combination with melamine resin can be used as anionic mediating surface molecular resin, and acrylic resin or epoxy resin can be used alone or in combination with urethane resin as cationic synthetic polymer resin to achieve transparency. , is a preferable resin from the viewpoint of color characteristics and the like. These resins are used in the form of being neutralized with an alkaline or acidic substance and solubilized in water so that they can be used in the electrodeposition method. That is, anionic synthetic polymer resins are neutralized with amines such as triethylamine, diethylamine, dimethylethanolamine, and diisopropanolamine, and inorganic alkalis such as ammonia and caustic potash. Zero-thionic synthetic polymer resins are neutralized with acetic acid, It is used after being neutralized with an acid such as formic acid, propionic acid, or lactic acid and then diluted in water as a water-dispersed or dissolved form.

The amount of neutralizing agent used is indicated by the MFIQ value and is determined by the following measurement method. This characteristic value is the stability of the electrodeposition bath, current efficiency, coating 1! This is an important characteristic value that greatly influences the finished state of EN and the state of the electrodeposited surface. For cationic electrodeposition baths, the range is 15 to 50, preferably 20 to 50.
It is 40.

Further, in an anionic electrodeposition bath, it is preferably 50 to 100 within a range of 40 to 130. Below each of the above lower limits, the stability of the electrodeposition bath may be impaired, and above each upper limit, current efficiency may decrease, resulting in deterioration of the finished state of the coating film, and elution or destruction of the surface to be coated. may occur.

The manufacturing methods for these polymer resins differ depending on their type, but we will explain one of the most important resins, thionic acrylic resin, as an example.Acrylic resins are made of acrylic esters, methacrylic esters, styrene, etc. Obtained by radical copolymerization of monomers containing vinyl groups. Its composition consists of (1) the amount of base in the resin to make it water-solubilized, and (11) the amount of functional group t! to give it reactivity. , (Ill) hardness, Ov) coating film performance, etc. Introduction of a base into the resin is glycidyl.

A method in which an oxirane group is introduced into the resin using acrylate or methacrylate, and an amine is added to this to attach a secondary or tertiary amino group, tertiary-butylaminoethyl methacrylate, dimethyl There is a method of using aminoacrylate or methacrylate such as amine ethyl methacrylate, or vinylpyridine. The degree of basicity is indicated by the base number of the resin, which is an important characteristic value as it greatly affects the degree of solubilization, electrodeposition characteristics, etc., and is usually 0.2 to 2.0, preferably 0.4 to 2.0. It is 1.0. If the base number is less than 0.02, the dispersibility in water may be poor and there may be a lack of stability.If it is more than 2.0, the current efficiency will decrease, and a colored layer may not be formed, the skin may become rough, or the conductivity of the electrode may deteriorate. It may destroy the thin film layer. Note that this value is not limited only to cationic acrylic resins, but is applicable to cationic resins in general. Furthermore, hydroxyl groups or amide groups may be introduced into the resin using hydroxyacrylate or acrylamide to impart water dispersion stability and reactivity. Once the monomer composition has been determined, the polymerization is usually carried out by solution polymerization in a hydrophilic solvent using a common radical intermediate initiator. The resulting resin has self-crosslinking properties, or is optionally used in combination with a crosslinking resin such as a urethane resin having blocked NGO groups.

Conductive ultrafine particles that provide conductivity to the coating film include ultrafine particles of oxide semiconductors such as tin oxide, indium oxide, antimony oxide, zinc oxide, and cadmium oxide, and chemically stable metals such as gold, silver, and nickel. ultrafine particles can be used. Each of these can be used alone or in combination, but considering the transparency of the coating film and the stability of the 'F11'4 bath, tin oxide or indium oxide is the most effective. It is preferable to use the metal in combination with other metals. These ultrafine particles must be used at visible wavelengths of 0.4 to 0.05 to 0.05 to 0.000, which is the visible wavelength, in order not to impair the transparency of the coating film.
It is necessary to disperse the particles to have an average particle size of 8 tones or less, and when the average particle size is 02 to 03 or less, it exhibits practically preferable transparency.

The content varies depending on the desired market conductivity of the coating film, the specific gravity of the particles, etc., but is 5 to 50% by weight, preferably 10 to 25% by weight, based on the solid content of the total composition. 5%
If it is less than 50%, the effect contributing to conductivity will be small, and if it exceeds 50%, it will be difficult to obtain a smooth and uniform coating film due to loss of flexibility as an electrodeposition property. The conductivity imparted as a coating provides a display effect with good characteristics without causing a drop in the effective voltage of the display element, especially when used in a display that operates at low voltage klA such as a liquid crystal display. is useful for
The specific resistance value of the coating film may be equal to or less than the electrical resistance value of the liquid crystal used, and is usually preferably 10 11 Ω·α or less.

Pigments or dyes are used as a color table that provides transparency and color to the coating film, but pigments are used to determine the transparency of the resulting coating film, and dyes are used to determine bath stability, electrodeposition characteristics, and durability of the coating film. You must choose one that does not cause any problems.

From this point of view, suitable pigments include organic pigments such as phthalocyanine-based and threne-based pigments, oxides such as iron oxide, and inorganic pigments, while oil-soluble or dispersible dyes are suitable as dyes. In order to obtain a good coating film, it is preferable to refine the pigments and other pigments used including such isoelectric ultrafine particles to remove impurities before use.

In addition, the composition of the present invention contains organic solvents that (1) provide a smooth coating film, (II) improve bath liquid stability, and (1) provide a smooth coating film.
) It may be added for the purpose of facilitating dispersion.

Hydrophilic solvents such as cellosolves such as ethyl, butyl, and methyl cellosolves, alcohols such as impropatol and butanol, glycols, and carbitols are mainly used, but in some cases, hydrophilic solvents such as quidylol, doluol, and mineral turpentine are used. Hydrophobic solvents can also be used.

Examples of auxiliary agents used include dispersants that improve the dispersibility of pigments, leveling agents that improve the smoothness of coating films, and antifoaming agents that stop foaming in the bath.

The composition of the present invention can be dispersed using a commonly used dispersing machine such as a sand mill, a pearl mill, a roll mill, or an attritor, but it must be dispersed sufficiently well in order to obtain transparency and smoothness of the coating film. The conductive ultrafine particles and pigments are then diluted with a solvent and mixed with a neutralized synthetic polymer resin. Next, auxiliary agents are added, and finally the mixture is diluted with pure water to a predetermined concentration, usually 4 to 25% in solids content, and then subjected to electrodeposition.

Polymer electrodeposition methods include cationic polymer electrodeposition method and anionic polymer electrodeposition method, both of which can be put to practical use, but the cationic polymer used in cationic polymer electrodeposition method Since it is inherently less hydrolyzable than anionic polymers, it affects the stability of electrodeposition baths. In addition, during electrodeposition, because a colored layer is deposited on the cathode side, and because a high current efficiency is obtained due to the composition, there is little electrolytic influence on the conductive thin film layer as an electrode. It has the advantage that an indium oxide conductive film, which is difficult to deposit, can be easily electrodeposited as a conductive thin film layer.

The present invention will be explained in detail below using Examples.

The middle part of the sentence is the weight part.

Example 1 Cationic electrodeposition liquids of the following three colors were prepared.

Blue Green Red Acrylic resin (manufactured by Shinto Paint Co., Ltd.) 60 parts 60 parts 60
Part Ethyl cellosolve 30 30 30 Isopropyl alcohol 3 3 3 Acetic acid (neutralizing agent) 1.8 1.8 1.8 Ion exchange water 875.2 875.2 875.2 Tin oxide (T-1
, made by Mitsubishi Metals Co., Ltd.) 10 10 10 Silver (ultrafine particles, Shinku Yakiniku Co., Ltd.) 5 5 5 Tin oxide, @ (ultrafine particles) and color chips were added to a mixed solution of 40 parts of acrylic resin and ethyl cellosolve while stirring. The pigments were added, mixed, and dispersed in a laboratory-grade mill (manufactured by Kodaira Seisakusho) until the pigment particle size was 0.3p or less.To measure the particle size, a Coulter Counter N4 was used to measure the particle size. Using.

Add the remaining acrylic resin and isopropyl alcohol to the above dispersion mixture and i. [After cooling, the mixture was neutralized with an acetic acid aqueous solution while stirring, and then diluted with ion-exchanged water.

The obtained bath liquid has an MEQ of 40, contains a total of 25% by weight of tin oxide and silver as conductive pigments in the solid content, and the volume solid state resistance of the colored layer obtained by electrodeposition is 10Ω.
It was G.

The acrylic resin used had a nonvolatile content of 75%, a base number of 1.0, and a viscosity of 60 poise (at 25°C).

The base number and MEQ value were measured by the following method.

Measurement of base number An unneutralized basic resin containing no acidic compounds is collected in an Erlenmeyer flask so that the solid content is about 1 gr. Add dioxane 60Ω and dissolve well (sometimes heating). Add 2-3 drops of methyl red, 1/ION-H
Titrate with CI, convert the ω number required to reach the discoloration point per 1g of basic resin, and use that value as the base number of the basic resin.

Measurement sample of MEQ value 20me was accurately weighed, and tetrahydrofuran 100
Add 1/10 N-alcoholic K and keep stirring
While dropping the OH solution, measure the pH value with a PH meter and draw a titration curve. From the two inflection points of the titration curve, find the midpoint and calculate the titration amount of 1/10N alcoholic KOH solution required to reach the midpoint. Next, the acid concentration is calculated using the NEQ formula.

XC f: 1/1N-potency S of alcoholic KOH solution
: Heavy adhesion of sample (gr) C: Residue of sample after heating Using these three color bath solutions, a stripe pattern as shown in FIG. 1 is created with a line width of 200. Red, green, blue 111 on Ifm
A transparent multicolored surface colored body with color coding of 1'1 was prepared.

The manufacturing method will be specifically described below.

■ Buttering process 1 is a transparent substrate made of glass, and an indium oxide transparent isoelectric film is formed on the transparent substrate by a spray coating method,
Next, the transparent conductive film is patterned into stripes by etching to obtain transparent electrodes 2.2', 2''.

■Electrodeposition process In the red electrodeposition bath prepared as described above, the transparent electrode 2.2
The transparent substrate 1 on which the electrodes ', 2'' are formed is immersed.The transparent electrodes 2 and 2', which are patterned in stripes, are selected from the electrodes 2' and 2'' to be colored in the same color, for example, 2, and that electrode is used as the cathode and the counter electrode. Apply a 10 to 40 V 'correction for 3 minutes between. At this time, a large current flows immediately after the current is turned on, but it gradually decreases and approaches zero. After energization is stopped, the transparent substrate 1 is pulled up and thoroughly washed with water to wash away the solution adhering to the portions to which no voltage or voltage is applied. After washing with water and drying, a highly transparent red colored layer is formed on the electrode to which voltage has been applied.

(2) Hardening process Next, the acrylic resin in the red colored layer formed by electrodeposition is baked to undergo a condensation reaction and harden. It is cured by baking in air at 175° C. for 30 minutes, but if you want to increase the fastness of the colored layer, baking for a longer time or under reduced pressure. The thickness of the colored layer after curing is 1
．． It was 5 μm.

Although the cured colored layer has a volume resistivity of 1010Ω・-, it is not conductive enough to cause redeposition, so even if it is immersed in an electrodeposition bath again and energized, redeposition and double dyeing will not occur. figure,
The formation of a colored layer for the second time and thereafter is realized by selecting a transparent electrode to be colored blue or green, and repeating the steps of electrodeposition and curing in the aforementioned electrodeposition bath of each color tone.

In this example, a red colored layer 3, a green colored layer 3', and a blue colored layer 3'' are formed on the transparent electrodes 2, 2', and 2'' respectively through a patterning process → red electrodeposition process → curing process → green colored layer 3''. It was manufactured using the following method: electrodeposition process → curing process → blue electrodeposition process → curing process, and was extremely simple. According to this method, if the desired precision is obtained in the first patterning process, there will be no deterioration of the dregs in the subsequent process, and even in this example, the transparent electrode 2
, 2', 2'' and the colored layers 3.3', 3'', there was no pattern shift or protrusion at all. Furthermore, the colored layers obtained were uniform, resistant to attack by acids, alkalis, various organic solvents, hot water, etc., and had sufficient strength against peeling. The pigment used is extremely stable in colored Jci, and even after 360 hours of carbon arc test, the initial light absorption rate was 95%.
It showed the above value and had excellent light resistance.

An example of the application of the conductive multicolored surface-colored body as shown in this example is that it is useful as a means to make display elements such as liquid crystal elements used in calculators, watches, etc. multicolored, and electrodes for electrodes are an example of this. It can be used as a display electrode, and its utility value is extremely limited. It is particularly advantageous as a multicolor means for high-precision, high-definition displays such as matrix drive elements, and since the colored layer has conductivity, it has a low cost. When applied to voltage-driven displays,
It also has the great advantage of not reducing the effective voltage of the display element.

Example 2 Striped transparent electrode in Example 1 2゜2/,
A multicolor surface-colored body was produced in the same manner as in Example 1, with the line width of 2// being 20 μm, and the same effects as in Example 1 were obtained.

This example has revealed that the present invention can also be applied to multicolor dividing means for optical systems that require higher precision and fineness than display elements, such as color filters for image pickup tubes.

Example 3 In Example 1, the transparent electrodes 2, 2', 2'/ were created using a tin oxide transparent conductive film, and then a multicolored surface colored body was created in the same manner as in Example 1. The effect was obtained.

Example 4 The following three colors of cationic electrodeposition bath liquids were prepared.

Blue Green Red acrylic resin (manufactured by Shinto Paint Co., Ltd.) 34.5 parts 34.5 parts 34.5 parts Ethyl cellosolve 17.0 17.0
17.0 Isopropyl alcohol 2.0 2.0 2
．． 0 Methyl Cellosolve 80.0 80.0 80.0
Acetic acid (neutralizing agent) ' 0.8 0.8 0.8 Ion exchange water 852.9 852.9 852.91000
．． 0 1000.0 1000.0 7.8 parts of tin oxide was added and mixed with stirring into a mixed solution of 3445 parts of the acrylic resin used in Example 1 and 17.0 parts of ethyl cellosolve,
The particles were dispersed using a laboratory sand grind mill (manufactured by Asada Iron Works Co., Ltd.) until the tin oxide particle size became 0.3 fi or less.

The particle size was measured using Coulter Counter N4.

After adding 2.0 parts of isopropyl alcohol to this mixture and stirring for 15 minutes, the mixture was neutralized with aqueous acetic acid and diluted with ion-exchanged water.

Meanwhile, 5.0 parts of each of blue, green, and red dyes were dissolved in 800 parts of methyl cellosolve under stirring. Adding this melt to an acrylic resin aqueous solution containing dispersed particles of tin oxide,
Cationic electrodeposition bath liquids were prepared in three colors: blue, green, and red. These three color bath liquids had MEQ = 35 and contained 20% by weight of tin oxide as a conductive pigment in the solid content. This 3
A multicolored surface-colored body was prepared in the same manner as in Example 1 using colored electrodeposition baths, and the same effects as in Example 1 were obtained.

Example 5 Anionic electrodeposition bath solutions of the following three colors were prepared.

Blue Green Red Butyl cellosolve 45 45 45 n-butanol 5 5 5 Triethylamine 4 4 4 Ion exchange water 851. 851 851 Non-volatile content 75
%, acid value 50 (acid value is K required to neutralize 1f of resin solid content)
(η number of OH), 40 parts of 60 parts of polyester resin with a viscosity of 60 voids (25°C) and 4 parts of butyl cellosolve.
5 parts, tin oxide, and phthalocyanine blue were dispersed using a laboratory dispersion machine, a sand grind mill (manufactured by Asada Tekkosho Co., Ltd.), until the pigment particle size became 0.3, tt.

A Coulter Counter N4 (manufactured by 1-Luther Counter Co., Ltd.) was used to measure the particle size. After adding the remaining polyester resin, melamine resin, and n-bup/-/l/ to the composition in which the pigment particle size was dispersed to 0.3 p or less and thoroughly mixing, the mixture was neutralized with triethylamine and poured into ion-exchanged water. diluted with

These three color bath solutions contained 15% by weight of tin oxide as a conductive pigment in the solid content, and the volume resistivity of the colored layer obtained by electrodeposition was 1010 Ω·0. The acid value was measured by the following method.

Method for Measuring Acid Value A fixed amount of resin is dissolved in a fixed amount of alcohol or ether, and the dissolved product is titrated with 172N potassium hydroxide using phenolphthalein as an indicator.

The number of pounds of potassium hydroxide required for titration is converted to resin solid content of 12, and this value is taken as the acid value.

Using these three colors of anion electrodeposition bath liquids, we fabricated a transparent multicolored surface-colored object with a stripe pattern as shown in Figure 1, which was color-coded in the order of red, green, and blue, with a line width of 200/'m. .

The manufacturing method will be specifically described below.

(2) Buttering step 1 is a transparent substrate made of glass, and a tin oxide transparent conductive film is formed on the transparent substrate by a spray coating method. The transparent conductive film is patterned into stripes by etching to obtain transparent electrodes 2°2', 2''.

■Electrodeposition process Transparent Fi2,
The transparent substrate 1 on which electrodes 2', 2" are formed is immersed. The transparent electrodes 2', 2', 2" patterned in stripes are dipped.
Select the electrodes that you want to color in the same color, for example, 2, and apply a voltage of 10 to 40 V between it and the counter electrode, using that electrode as an anode.
Apply for minutes.

At this time, a large current flows immediately after the current is turned on, but it gradually decreases and approaches zero. After energizing, transparent substrate 1
Pull it up and wash it thoroughly with water to wash away the solution that has adhered to the parts where no voltage is applied. After washing with water and drying, a highly transparent red colored layer is formed on the electrode to which voltage has been applied.

(2) Curing process Next, the polyester resin and melamine resin in the colored layer formed by electrodeposition are baked to undergo a condensation reaction and cured. It will harden if baked in air at 175℃ for 30 minutes, but if you want to increase the fastness of red colored J-,
The baking time should be increased or the pressure should be reduced. The thickness of the red colored layer after curing was 1.5 meters.

Thereafter, in the same manner as described above, the curing process was repeated for the remaining two Buddhist statues and green electric lamps to obtain the same effect as in Example 1.

Comparative example 1 The following cationic electrodeposition solution was prepared.

Acrylic resin (manufactured by Shinto Paint Co., Ltd.) 60.0 parts Ethyl cellosolve 30.0 Isopropyl alcohol 3.0 Acetic acid (neutralizing agent) 1.8 Ion exchange water 875.2 Tin oxide (T-1 + Mitsubishi Metals Co., Ltd.) 10 .0 Silver (ultrafine powder, manufactured by Shinku Yakiniku Co., Ltd.) 5.0 1000.0 A special resin with a non-volatile content of 75%, a base value of 3.0, and a viscosity of 100 poise (25°C) was used as the cationic acrylic resin. MEiQ was 40 in the same manner as in Example 1 except for
A bath liquid was prepared.

A display substrate on which display electrodes were formed using the indium oxide transparent conductive film used in Example 1 was immersed in this bath solution, and electrodeposition was performed in the same manner as in Example 1. The layer had rough skin and was unsuitable for practical use.

Comparative example 2 The following cationic electrodeposition bath solution was prepared.

Acrylic resin (manufactured by Shinto Paint Co., Ltd.) 60.0 parts Ethyl cellosolve 30.0 Impropinogelcol 3.0 Acetic acid (neutralizing agent) 1.8 Ion exchange water 875.2 Tin oxide (T-1, manufactured by Mitsubishi Metals Co., Ltd.) ) 100 silver (ultrafine particles, manufactured by Shinku Yakiniku Co., Ltd.) 5.0 Conducted except that the cationic acrylic resin used was a resin with 75% non-silica, base number 0.1, and viscosity 40 poise (25°C) A bath solution having an MEQ of 40 was prepared in the same manner as in Example 1.

This bath liquid was extremely unstable, containing aggregates of acrylic resin, and was not suitable for practical use.

Comparative example 3 The following cationic electrodeposition bath was prepared.

Acrylic resin (manufactured by Shinto Paint Co., Ltd.) 87.0 parts Ethyl cellosolve 43.5 Isopropyl alcohol 4.0 Acetic acid (neutralizing agent) 2. Fion-exchanged water 832.8 Tin oxide (T-1, manufactured by Mitsubishi Metals Co., Ltd.)' 10.0 Silver (ultrafine particles, manufactured by Shinku Yakiniku Co., Ltd.) 5.0 iooo.

The bath was prepared in the same manner as in Example 1 except that the amount of acetic acid was different, and a cationic electrodeposition liquid having an htEQ of 60 was obtained.

A transparent electrode formed from the indium oxide transparent electrode film used in Example 1 was immersed in this bath solution, and electrodeposition was performed in the same manner as in Example 1, but the colored layer obtained was rough on the skin. This caused a problem in practical use.

Comparative example 4 The following cationic electrodeposition bath was prepared.

Acrylic resin (manufactured by Shinto Paint Co., Ltd.) 87.0 parts Ethyl cellosolve 43.5 Inpropyl alcohol 4.0 Acetic acid (neutralizing agent) 0.45 Ion exchange water 835.05 Tin oxide (T-1, manufactured by Mitsubishi Metals Co., Ltd.) ) 10.0 silver (ultrafine powder, manufactured by Shinku Yakiniku Co., Ltd.) 5.0 The bath was prepared in the same manner as in Example 1 except that the amount of acetic acid was different, and a cationic electrodeposition solution with an MBQ of 10 was obtained. However, this bath solution was extremely unstable and contained aggregates of acrylic (σ1 fat) and was not suitable for practical use.

Effects of the Invention As specifically described in the examples, according to the present invention, a multicolored surface-colored body having conductivity that requires high precision and fineness can be manufactured by a simple method, and the precision can be improved. is superior in principle to other methods. In addition, since the colored layer of the resulting multicolor surface-colored body has conductivity, it has the great advantage of not reducing the effective voltage of the display element when applied to a low-voltage drive display. ,
The present invention is expected to be applied not only to optical multicolor separation means such as image pickup tubes, but also to a wide variety of other fields.

[Brief explanation of drawings]

FIG. 1 is a plan view of a multicolored surface colored body according to the present invention, and FIG. 2 is a sectional view thereof. 1-m-substrate 2.2', 2"--one electrode 3°3',
3"-m-Colored layer patent applicant Seiko Electronics Co., Ltd. Shinto Paint Co., Ltd. Figure 1, page 1 continued 0 Inventor Yutaka Sano @ Inventor Tera 1) Yumiko @ Inventor Naoki Kato @ Invention Person Suzuki A2 [Phase] Inventor Jun Yasukawa @ Inventor 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., Tokyo 6-31-1 Kameido, Koto-ku Seiko Electronics Co., Ltd. 3-1-7 Yamanone, Zushi City 2-1 Higashi Minami, Chigasaki City 5-1-1 Narashino Narashino 6 Kanamachi, Katsushika-ku, Tokyo Chome 6-14 3-7-24 Higashi-Narashino, Narashino City Procedural amendment (voluntary) June 28, 1980 Director General of the Patent Office Waka Aiwa Failure 1, Indication of case 1981 Special F+; Application No. 40788 2. Title of the invention: Method for producing a multi-color colored body with conductive surface. Contents (1) Insert "Kl" next to "to the extent applicable" on page 9, line 13 of the specification. (2) On page 9, line 15, after “to the extent applicable”, “
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Correct ul as 50 ho 11. (4) Page 12, line 16 “5% Zhu7i:'3 J”
4% Shu 7 Fu” is corrected. (5) In the 13th summer, line 5, rlO1lΩ"CIIIJ" is corrected to "rlO'Ω・α". (6) Correct ``color table'' in line 6 of Wataru 13 to read ``irotai.''('r)"," in the Q next to "bath stability" on page 13, line 9.
4iir people. (8) Delete "," next to "oxide" on page 13, line 12. (9) Insert "," after "pigment ga" on page 13, line 13. (10) Page 13, lines 16 to 17 “For urinating”
Insert "," after. (11) lr+J, page 15, line 3, insert "1-1" next to "It will be served". (12) Insert "," next to "The cationic polymer" on page 15, line 4. (13) On page 26, line 2, "7 talocyanine blue" is corrected to "each pigment."that's all

Claims (1)

[Claims] 1. Forming a plurality of conductive layers arranged insulated from each other on a substrate, and then depositing a colored cationic or anionic polymer selected from a colored cationic or anionic polymer electrodeposition bath on the conductive layers. A multicolored surface-colored product characterized by forming a colored layer having electrical conductivity, and then repeating the above operation using a cationic or anionic electrodeposition bath of a different color from the polymer electrodeposition bath. manufacturing method. 2. The method according to claim 1, wherein the base number of the polymer resin used in the cationic polymer electrodeposition bath is 02 to 2.0, and the MEQ value of the electrodeposition bath is 15 to 50. A method for producing a multicolored surface colored object.