JPS60186803A - Multi-color display device and its production - Google Patents

Abstract

PURPOSE:To provide a high grade of display to the titled device by using the multi-color filter having the multi-color layers consisting of a cationic or anionic high polymer resin having <=10<12>OMEGAcm intrinsic resistance on the plural conductive layers formed isolatedly on a base material. CONSTITUTION:A transparent tin oxide conductive film is formed by a spray coating method on a display substrate 8 consisting of a transparent material and the conductive film is patterned to a stripe shape by etching to obtain display electrodes 9. The substrate 8 is dipped in an electrodepositing bath and the electrodes desired to be colored to the same color are selected. For example, 20V voltage is impressed for 3min to said electrodes as anode. The substrate 8 is then pulled up and is thoroughly rinsed to wash away the soln. sticking to the part where the voltage is not impressed. The polyester resin and melamine resin in the colored layer formed by the electrodeposition are then baked to effect a condensation reaction by which said resins are cured.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a multicolor display device using a color filter and a method for manufacturing the same, and in particular, to a high conductivity film having a specific resistance of 1011 ΩC or less and formed by electrodeposition. The present invention relates to a multicolor display device having a color filter made of a molecular resin layer and a method for manufacturing the same.

BACKGROUND OF THE INVENTION FIG. 1 shows a cross-sectional view of an example of a multicolor display device to which a conventional color filter is applied.

In FIG. 1, l is a transparent substrate, 2, 2', 2' are display electrodes made of transparent conductive layers patterned with arbitrary figures or characters, and 3, 3', 3'' are display electrodes 2.
, 2', a color filter formed in close contact with the surfaces of 2', 4 a transparent counter electrode, 5 a transparent counter substrate, 6
is a spacer. In such a multicolor display device, 2
A space 7 sandwiched between the two substrates 1 and 5 is filled with a substance, such as a liquid crystal or an electrochromic material, that functions as an optical shutter that opens and closes when voltage is applied, and the color filters 3, 3', 3' are colored in different colors. Once formed, multicolor display is possible by selectively applying a voltage between the display electrodes 2, 2°, 21 and the counter electrode 4.

Multicolor display using color filters is simple, easy to obtain any color tone, and can be used in combination with various display materials and methods, so it has extremely large practical effects.

However, when manufacturing a multicolor display device that uses color filters, it is necessary to manufacture the display electrode pattern so that there is no misalignment between the pattern of the display electrode and the pattern of the color filter formed on the surface of the display electrode. No. In particular, when attempting to realize a color graphic display using fine patterns of three primary colors, pattern matching between display electrodes and color filters is an important problem that is difficult to manufacture. In addition, the chromaticity required to create multiple colors is a factor that complicates the process, especially when trying to achieve coloring by dyeing with dyes. This process becomes even more complicated. Furthermore, the resist dyeing technology itself is a difficult issue that must be considered individually for each dye.

Generally, the way to create a color filter is as follows:
Methods using methods such as screen printing and photophosphorography are being considered.

Screen printing does not require resist dyeing, but there is a limit to how fine the pattern can be, and the more colors there are, the worse the accuracy of the printing position becomes, resulting in misalignment with the displayed pattern. Although it is possible to create fine patterns using photolithography, it is necessary to go through one photolithography process each time the color is changed, and a resist dyeing method that prevents double dyeing is required, making the process extremely complicated. Therefore, the advantage of being a simple means for multicoloring is lost.

Therefore, the present inventors proposed a simple method in Japanese Patent Application No. 57-233933 that allows the display pattern to be made finely, without pattern shift even if the pattern is changed, and without the need for special resist dyeing. We proposed a method for manufacturing a multicolor display device using a robust color filter using a polymer resin electrodeposition method.

OBJECTS OF THE INVENTION An object of the present invention is to provide a method for further improving the multicolor display device using a color filter produced by the above-mentioned polymer resin electrodeposition method.

When a color filter is used in a low-voltage display such as a liquid crystal display, the color filter acts as an insulating film, 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 solves the above problems by making the resistance value of the color filter less than the resistance value of the liquid crystal, that is, less than 10ItQcI11.

To this end, we used a conductive thin film layer on a substrate as an electrode, and used a color filter obtained by a polymer resin electrodeposition method from a polymer resin electrodeposition solution containing an electrodepositable polymer resin, a dye, and conductive ultrafine particles. Manufactures multicolor display devices.

To make the color filter used in the present invention, the conductive thin film layer is subjected to desired flattening by vapor deposition using a mask, sputtering, or etching, so that the polymer resin, pigment, and conductive ultrafine particles are exposed to a voltage. It is possible to selectively electrodeposit on the conductive portions to which the coloring layer is applied, and form a colored layer without shifting the pattern position. Furthermore, since this operation is repeated, a colored layer is not formed again on the part that has been electrodeposited once, so it is possible to easily create multiple colors.

Furthermore, since the colored layer formed has conductivity, even if the color filter according to the present invention is used, for example, in a low-voltage-driven display, it has the advantage of not reducing the effective voltage of the display element.

The substrate used in this method only needs to have an insulating surface, and by selecting a conductive thin film layer that has good adhesion to the substrate, the material 1. There are no restrictions regarding the shape.

Both anionic and cationic electrodepositable polymer resins can be used, but since cationic polymer resins are deposited on the cathode, the material of the conductive thin film layer where the colored layer is originally formed must be selected. It has characteristics such as being able to be used widely, having high current efficiency, and having a stable bath solution.

Structure of the Invention Below, an example of a method for forming a colored layer having electrical conductivity by a polymer resin electrodeposition method, which is an important point of the present invention, will be described.

In this method, first, as described above, a conductive thin film layer is patterned on a glass substrate as an insulating substrate (hereinafter referred to as a transparent conductive pattern).

Second, platinum was placed in a polymer resin electrodeposition bath prepared by diluting a polymer resin electrodeposition composition containing a dye and conductive ultrafine particles with pure water to a solid content of approximately 4 to 25% by weight and M1%. A counter electrode made of stainless steel or the like and a glass substrate with a transparent conductive pattern shown in L are immersed in the liquid. Next, place a pattern between the transparent electrode pattern to be colored and the counter electrode as a cathode in the case of cationic resin electrodeposition method, or as an anode in the case of anionic resin electrodeposition method.
Apply a DC voltage of 00■. As a result of this application, a polymer (fatty electrodeposition composition) containing a dye and conductive ultrafine particles migrates only on the pattern to which voltage is applied, depositing as a coating film and coloring the transparent electrode pattern. This is done by adjusting electrodeposition conditions such as voltage, electrodeposition time, and liquid temperature.

The normal dry film thickness is 5 tones or less. Electrodeposition time is usually 5~
180 seconds of liquid wetting is performed at a liquid temperature of 30°C.

After the electrodeposition time has elapsed to achieve the required film thickness, turn off the electricity.
The glass substrate is removed from the bath, the remaining bath liquid is thoroughly washed with pure water, and the coating is cured by heating.

In this way, a conductive transparent electrode pattern colored in one color is produced. The third is, for example, when making a multicolor filter with three colors of red, green, and blue.
The coloring process is repeated for each of the transparent electrode patterns that require coloring for the other two colors. As described above, a three-color conductive multicolor filter is produced by the polymer resin electrodeposition method.

This method does not require a photolithography process when coloring, and does not require resist dyeing treatment, so the process is simple, the transparent electrode pattern and the colored layer match, and the fine pattern is colored. This method fully overcomes the drawbacks of photography and printing methods, such as the fact that printing is difficult.

Next, the polymer resin electrodeposition liquid used in the polymer resin electrodeposition method, which is an important point of the present invention, will be explained. This configuration is (
1) Film-forming components of the coating film include an anionic or cationic synthetic polymer resin, (H) conductive ultrafine particles that impart conductivity to the coating film, and (Il+) that imparts transparency and color to the coating film. It consists of dyes such as pigments and dyes, and in addition, as bath components, Gy) organic solvents used to adjust the stability of mMY raw materials and bath solutions and to facilitate manufacturing, and (v) synthetic polymer resins. It consists of a neutralizing agent to make it soluble in the liquid, and various auxiliary agents to improve the electrodeposition properties of the coating film surface, stability of the bath solution, etc.

The configuration contents will be explained in detail below.

Synthetic polymer resins used as film-forming components of coating films include acrylic resins, polyester resins, maleated oil resins, polybutadiene resins, and anionic synthetic polymer resins.
Epoxy resins are used alone or in combination with crosslinkable resins such as melamine resins, phenol resins, and urethane resins. In addition, cationic synthetic polymer resins include acrylic resin, epoxy resin,
Examples include urethane resins, polybutadiene resins, and polyamide resins, which are used alone or in combination with crosslinkable resins such as urethane resins and polyester resins. As anionic synthetic polymer resins, acrylic resins and polyester resins can be used alone or in combination with melamine resins, and as cationic synthetic polymer resins, acrylic resins and epoxy resins can be used alone or as mixtures, or in combination with urethane resins. It is a preferable resin from the viewpoint of transparency, color characteristics, etc. 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, the anionic synthetic polymer resin is neutralized with amines such as triethylamine, diethylamine, dimethylethanolamine, and diisopropanolamine, and inorganic alkalis such as ammonia and caustic potash. Cationic synthetic polymer resins include acetic acid, formic acid,
It is used after being neutralized with an acid such as propionic acid or lactic acid and solubilized in water, or diluted in water as a water-dispersed or dissolved form. The amount of neutralizing agent used is indicated by the MEQ value. The measurement method is described in the examples. This characteristic value is an important characteristic value because it has a large effect on the stability, current efficiency, finish condition of the coating film, and condition of the surface to be electrodeposited. is preferably 20 to 40 within the applicable range. In addition, in an anionic electrodeposition bath, it is preferably 50 to 100, within a range of 40 to 130. If it is below the lower limit, the stability of the electrodeposition bath may be impaired, and if it exceeds the upper limit, the current efficiency will decrease, resulting in deterioration of the finish of the coating film.
This may cause elution or destruction of the painted surface.

Although the manufacturing method for these polymer resins differs depending on their type, cationic acrylic resin, which is one of the most important resins, will be explained as an example. Acrylic resins are obtained by radical copolymerization of vinyl group-containing monomers such as acrylic esters, methacrylic esters, and styrene. The composition is determined by considering (1) the amount of base in the resin to make it water-soluble, (11) the amount of functional groups to impart reactivity, (11) hardness, h) coating performance, etc. A base can be introduced into the resin by introducing an oxirane group into the resin using glycidyl acrylate or methacrylate, and adding an amine to this to obtain a secondary or tertiary amino group. having,
There is a method of using aminoacrylates or methacrylates such as tert-butylaminoethyl methacrylate and dimethylamine ethyl methacrylate, or vinylpyridine. The degree of basicity is indicated by the base number of the resin, and it is an important characteristic value because it has a great influence on the degree of solubilization, electrodeposition characteristics, etc., and is usually 0.2 to 2.0, preferably 0.4 to 2.0. 1, 0. If the base number is less than 0.2, the dispersibility in water may be poor and stability may be lacking;
．． If it is more than 0, the current efficiency decreases, and a colored layer may not be formed, rough skin may occur, or the conductive thin film layer of the electrode may be destroyed.

Note that this value is not limited only to cationic acrylic resins, but is applicable to cationic resins in general. Additionally, hydroxyl groups and amide groups are introduced into the resin by using hydroxyacrylate and acrylamide to provide water dispersion stability and reactivity. Once the monomer composition has been determined, polymerization is usually carried out in a hydrophilic solvent by radical polymerization.The conductive ultrafine particles that give electrical conductivity to coatings include tin oxide, indium oxide, antimony oxide, zinc oxide, and cadmium oxide. There are ultrafine particles of physical semiconductors and ultrafine particles of chemically stable metals such as gold, silver, and nickel. Each of these can be used alone or in combination; however, considering the transparency of the coating film and the stability of the electrodeposition bath, tin oxide or indium oxide is the most effective, and they can be used alone, in a mixture, or in combination with them. Mixtures with other metals are preferred. In order not to impair the transparency of the coating film, these ultrafine particles must be dispersed to an average particle size of 0.4 to 0.8/II or less, which is the wavelength of visibility, and the average particle size is 0. .2
When it is 0.3 tones or less, it exhibits transparency that is preferable for practical use. The content varies depending on the desired conductivity of the coating film, the specific gravity of the particles, etc., but the content ranges from 5 to 50% in the solid content of the total composition.
ffiffi%, preferably 10 to 25% by weight.

If it is less than 5%, the effect of reducing the conductivity will be poor, and if the
If it exceeds %, the brightness as an electrodeposition property will be impaired and it will be difficult to obtain a smooth and uniform coating film. The conductivity applied as a coating film is particularly effective when used in displays driven at low voltage, such as liquid crystal displays, in order to provide a good display effect without causing a drop in the effective voltage of the display element. useful and
The specific resistance value of the coating film should be equal to or less than the electrical resistance value of the liquid crystal used, and usually IQ1! Ω or less is preferable.

Pigments or dyes are used as pigments that are transparent and colorable to the coating film, but the transparency of the resulting coating film is important for pigments, and the bath stability, electrodeposition properties, and durability of the coating film are important for dyes. You must choose one that does not cause any problems.

From this point of view, suitable pigments are organic pigments such as phthalocyanine and threnic pigments, and oxide inorganic pigments such as iron oxide, and suitable dyes are oil-soluble or dispersible dyes.

In order to obtain a good coating film, it is preferable that pigments and other pigments used including such conductive ultrafine particles be purified to remove impurities before use.

In addition, the composition of the present invention contains organic solvents that (1) provide a smooth coating film, (11) improve bath liquid stability, and (Il
+1 Added for the purpose of facilitating dispersion.

The main types of solvents used are cellosolves such as ethyl, butyl, and methyl cellosolve, alcohols such as Impropatol and Butamele, and hydrophilic solvents such as glycol and carbitol.
Hydrophobic solvents such as doluol and mineral turpentine may 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, pearl mill, roll mill, or attritor, but it must be sufficiently well dispersed to maintain the transparency and smoothness of the coating film. The conductive ultrafine particles and pigments are then diluted with a solvent and mixed with the neutralized synthetic polymer resin. Next, auxiliary agents are added, and finally, the mixture is diluted with pure water to a predetermined concentration, usually about 4 to 25% solids content, and then subjected to electrodeposition.

The polymer resin electrodeposition method includes a cationic polymer resin electrodeposition method and an anionic polymer resin electrodeposition method. Although both can be put to practical use, the cationic polymer resin used in the cationic polymer resin electrodeposition method is inherently less hydrolyzable than the anionic polymer resin, so the stability of the electrodeposition bath may be affected. In addition, during electrodeposition, the cationic electrode deposition method deposits a colored layer on the cathode side, and because it provides a high current efficiency due to its composition, the electrolytic influence on the conductive thin film layer as an electrode is reduced. However, it has the advantage that an indium oxide conductive film, which is difficult to electrodeposit using an anionic polymer resin, can be easily electrodeposited as a conductive thin film layer.

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

Unless otherwise specified in a patent, all parts are by weight.

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

Acrylic resin (manufactured by Shinto Paint Co., Ltd.) 60 parts 60 parts
60 parts Ethyl cellosolve 3.0 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 Oxidation @ (T
-1 Mitsubishi Metals fM) 10 10 10 Silver (ultrafine particles,
Vacuum Metallurgy Company 5 5 51000 1000 100
0 In a mixed solution of 40 parts of acrylic resin and ethyl cellosolve,
Tin oxide, silver (ultrafine particles), and pigment were added and mixed with stirring, and dispersed in a laboratory three-roll mill (manufactured by Kodaira Seisakusho Co., Ltd.) until the number of pigment particles was 0.3 or less. A Coulter Counter N4 was used to measure the particle size.

The remaining acrylic resin and isopropyl alcohol were added to the above dispersion mixture and stirred for 15 minutes, and then neutralized with an acetic acid aqueous solution while stirring and diluted with ion-exchanged water.

The obtained bath liquid had an MEq of 40, contained tin oxide as a conductive pigment, and silver in a total of 25% by weight in the solid content, and the volume resistivity of the colored layer obtained by electrodeposition was 10.
", QCII+.The special characteristics of the acrylic resin used were: non-volatile content of 75%, base number of 1.0, viscosity of 60 poise (
25°C).

Base number and MFiQ 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 fr. Add 5Qcc of dioxane and dissolve well (sometimes heating). 'CC number' required to reach methyl red discoloration point
Basic resin 1? It is converted per r, and that value is taken as the base number of the basic resin.

Precisely weigh 20 ml of a measurement sample of MEQ, and while dropping the tetrahydrofural KOHi@ solution, measure the pH value with a pH meter and draw a titration curve. Find the midpoint between the two inflection points of the titration curve and calculate the distance to the midpoint. Then, the acid concentration is calculated using the MQ calculation formula.

xC No Teki Souhi←4 S: Weight of sample (yr) 0: heating residue of sample A multicolor display device was created using the above three color bath liquids.

FIG. 2 is a sectional view of a multicolor display device to which the method of manufacturing a color filter according to the present invention is applied.

Hereinafter, a method for manufacturing a multicolor display device as shown in FIG. 2 will be specifically described.

(2) Patterning step 7 is a display substrate made of a transparent material, and an indium oxide transparent conductive film is formed on the display substrate by a spray coating method. The transparent conductive film is patterned into stripes by etching to obtain display electrodes 9.

■Electrodeposition process Display electrode 9 is placed in the cationic electrodeposition bath prepared as described above.
The display substrate 8 is immersed.Select the electrodes that you want to color in the same color in the striped patterned display πtt?it9, and apply a voltage of 20V to the selected electrodes as cathodes. Apply electricity for 3 minutes. After energizing, pull up the display substrate 8 and wash it thoroughly with water to wash away the solution adhering to the areas where voltage is not applied. After washing with water and drying, the electrodes to which voltage was applied will have good transparency. A colored layer is formed.

(2) Curing process Next, the acrylic resin in the colored layer formed by electrodeposition is cured by baking to cause a crosslinking reaction. The colored layer is completely cured by baking in air at 175°C for 30 minutes. The cured colored layer has a volume resistivity of 10'.

Although it has a conductivity of Ωα, it is not conductive enough to cause redeposition, so even if it is immersed in an electrodeposition bath again, electrodeposition will no longer occur, so for the formation of colored layers from the second time onwards, This is achieved by selecting a display electrode for another color again and repeating the process of electrodeposition and curing in an electrodeposition bath in which pigments of different colors are dispersed.

As described above, in this embodiment, the transparent electrode 9 having a transparent conductive film made of indium oxide is used to form 200. ”
? FL width stripe-shaped color filter 10 is manufactured by the following method: patterning process → red electrode electrodeposition process → curing process → blue electrode electrodeposition process → curing process → green electrode electrodeposition process → curing process. It was easy to do. The obtained color filter showed no color shift, was uniform, and had properties that were not easily affected by acids, alkalis, various organic solvents, hot water, and the like. Furthermore, the pigment used was extremely stable in the colored layer, and even after 360 hours of the carbon arc test, it exhibited an initial light absorption rate of 95 parts or more, and had excellent light resistance.

In this way, the color filter 10 connects the display electrodes 9-
The display substrate 8 is integrated with a transparent counter substrate 12 on which a transparent counter electrode 11 is formed in a stripe shape through a spacer 13 so that the stripes of the display electrode 9 and the counter electrode 11 intersect at right angles. and configure the cells. 'f'N-FEM liquid crystal was filled in the cell as the display material 14 to produce a multicolor liquid crystal display device. In this case, a voltage is applied between the display electrode 9 and the counter electrode 11, the cell is sandwiched between a polarizer and an analyzer whose transmission axes are parallel, and when viewed from the direction of the display substrate 8 or the counter substrate 12, the cell is transparent. The color of the color filter 10 is displayed and becomes black when the voltage application is stopped. Light is irradiated from the direction of the counter substrate 12 (then, since the cell has good transparency, the color of the color filter 10 is displayed more effectively).

Voltage in the electro-optical characteristics of the multicolor display device of this example -
The transmittance characteristic measurement results are shown in FIG. 3 by curve a. For comparison, Figure 3 shows the voltage-transmittance characteristic measurement results of the liquid crystal material itself when no color filter is used.Curve b1The voltage-transparency measurement results when using a conventional color filter that does not provide conductivity. shows curve C. As can be seen from FIG. 3, by setting the resistance value of the color filter to 101θΩ1, it became possible to reduce the drive voltage by 0.3 to 0.5V and improve the abruptness of the rise in transmittance.

That is, although the manufacturing method of the multicolor display device of this embodiment is a simple manufacturing method, it is possible to obtain a color filter with a fine pattern without impairing the display quality, and moreover, it is possible to obtain a highly reliable low voltage matrix Pa. It has now been found that there is a method suitable for providing a dynamic color graphics display device.

Example 2 The display material 14 in Example 1 is a negative type guest host liquid crystal using dichroic colors such as black, and the display substrate 8 is a white material (white ceramic). Created a liquid crystal display device. In this case, the display electrode 9
A voltage is applied between the color filter 1 and the counter electrode 11, and when viewed from the direction of the transparent counter substrate 12 through the polarizing plate, the color filter 1
The color 0 is displayed brightly, and when the voltage application is stopped, it becomes black, which is the color of the dichroic dye in the liquid crystal. In this example as well, the same effects as in Example 1 were obtained.

Example 3 In Example 1, a tin oxide transparent conductive film was formed on a display substrate made of a transparent material by the spray coating method, and this transparent conductive film was patterned into stripes by etching to form display electrodes. A multicolor display device was manufactured in the same manner as in Example 1, and the same effects as in Example 1 were obtained.

Example 4 Anionic electrodeposition bath solutions of the following three colors were prepared.

Blue Green Red Polyester resin (manufactured by Shinto Paint Co., Ltd.) 60 parts 60 parts
60 parts Butyl cellosolve 45 45 45 n-butanol 5 5 5 Triethylamine 4 4 4 Iden-exchanged water 851 851 8511000 10
00 1000 Non-volatile content 75%, acid value 50 (acid value is the η number of KOH required to neutralize resin solid content 12), viscosity 60 poise (2
5%'C) of 60 parts by weight of polyester resin (hereinafter abbreviated as "parts"), 40 parts of butyl cellosolve and 45 parts of butyl cellosolve, and
Tin oxide and phthalocyanine blue were mixed using a laboratory dispersion machine, a sand grind mill (manufactured by Asada Iron Works Co., Ltd.) until the pigment particle size was 0.
．． It spread out until there were only three voices. Coulter is used to measure particle size.
Counter N4 (manufactured by Coulter Counter) was used.

The remaining polyester resin, melamine resin, and n-butanol were added to the composition in which the pigment particle size was dispersed to 0.3/1 or less, and the mixture was sufficiently mixed, neutralized with triethylamine, and diluted with ion-exchanged water.

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 101 OΩ1.

Using this bath liquid, a multicolor display device as shown in FIG. 2 was manufactured by the following method.

(2) Patterning step 8 is a display substrate made of a transparent material, and a tin oxide transparent conductive film is formed on the display substrate by a spray coating method. The transparent conductive +1'J is patterned into stripes by etching to obtain display electrodes 9.

(2) Electrodeposition step The display substrate 8 on which the display electrodes 9 are formed is immersed in the electrodeposition bath prepared as described above. Among the display electrodes 9 patterned into stripes, electrodes to be colored in the same color are selected, and a voltage of 20 V is applied for 3 minutes using the selected electrodes as anodes. After energization, the display substrate 8 is pulled up and thoroughly washed with water to wash away the solution adhering to the areas to which no voltage is applied. After washing with water and drying, a highly transparent colored layer is formed on the electrode to which pressure 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. The colored layer is completely cured by baking in air at 175°C for 30 minutes.

Thereafter, a multicolor display device was manufactured in the same manner as in Example 1, and the same effects as in Example 1 were obtained.

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

Polyester Akisashi (manufactured by Kagura Paint Co., Ltd.) 25.5 parts 25
．． 5 parts 25.5 parts Butyl cellosolve 21.0 21
．． 0 21. On-butanol 2.5 2.5 2.
5 Methyl cellosolve 8'0.0 80.0 80.0
Triethylamine 1.7 1.7 1. Fionic exchange water 850.0 850.0 850.0 Tin oxide 7.
8 7-8 7.8 1000 1000 1000 25.5 parts of the polyester resin used in Example 5, 21.0 parts of Butylseron Lube, and tin oxide were kneaded, and this mixture was mixed with a laboratory sand grind mill (manufactured by Asada Iron Works Co., Ltd.). ) until the particle size of tin oxide was 0.3 mm or less. Coulter Counter N4 (manufactured by Coulter Counter Co., Ltd.) was used to measure the particle size.

After adding 6.5 parts of melamine resin and 2.5 parts of n-butanol to a composition in which tin oxide is dispersed to a particle size of 0.3/1 or less and mixing thoroughly, triethylamine is added dropwise, and after further mixing, It was diluted with ion-exchanged water to a predetermined concentration.

Meanwhile, 5.0 parts of each of blue, green, and red dyes were dissolved in 800 parts of methyl cellosolve under stirring. This melt contains the previously prepared dispersed particles of tin oxide.

In addition to polyester-melamine resin aqueous solution, blue, green,
Electrodeposition bath liquids in three colors of red were prepared. These three color bath liquids are
The solid content contains 20ftKll1% of tin oxide as a conductive pigment. Example 5 Using these three color electrodeposition baths
A multicolor display device was produced in the same manner as in Example 5, and the same effects as in Example 5 were obtained.

Comparative example 1 Anionic electrodeposition bath solutions of the following three colors were prepared.

Polyester resin (Shinto Nurisha-4) 600 copies 600
Parts 600 parts Butyl cellosolve 45.0 45.0
45.0!1-Butanol 5.0 5.0 5.0
Triethylamine 4.0 ' 4.0 4.0 Ion exchange water 860.9 860.9 860.9 Tin oxide (
T-1 Sanbin Metal Co., Ltd.) 2.1 2.1 2.1100
0.0 100Q and 0 1000.0 baths were prepared in the same manner as in Example 5 except that the tin oxide was different.

These bath solutions contained 3.0% 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 1 o 14 ΩG. A multicolor display device was produced in the same manner as in Example 5 using colored electrodeposition baths, but because the conductivity imparted to the color filter layer was not sufficient, the curve d in FIG. The electro-optical characteristics of a multicolor display device, such as the one shown in FIG.
Still, it had no effect.

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

Acrylic resin (made by Shinto Paint Co., Ltd.) 60.0 parts Ethyl cellosolve 30.0 Isopropyl alcohol 3.0 Acetic acid (degree of neutralization) 1.8 Ion exchange water 875.2 Tin oxide (T-1 made by Mitsubishi Metals Co., Ltd.) 10 .0 silver (ultrafine particles, manufactured by Shinku Yakini Co., Ltd.) 5. O Phthalocyanine Blue (SR-150G' manufactured by Sanyo Shiki Co., Ltd.) 15.01000.0 Except for using a resin with a nonvolatile content of 75%, a base number of 0.1, and a viscosity of 40 voids (25°C) as the cationic acrylic resin, A bath solution having an MQ of 40 was prepared in the same manner as in Example 1.

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

Comparative example 3 The following cationic electrodeposition solution was prepared.

Acrylic resin (Shinto Toyo Co., Ltd.'ju) 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 manufactured by Mitsubishi Yomon Co., Ltd.) ) 10.0 Silver (Ultrafine Particles Shinku Yakinsha @) 5.0iooo.

The same method as in Example 1 was used except that a special resin with a nonvolatile content of 75%, a base number of 3.0, and a viscosity of 100 poise (25°C) was used as the cationic acrylic resin.
A bath solution of 0 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 colored layer had rough skin and was poor 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 Isopropyl alcohol 4.0 Acetic acid (neutralizing agent) 2. ion-exchanged water 832.8 Tin oxide (T-1 manufactured by Mitsubishi Metals) 100 silver (ultrafine particles)
Shinku Yakinsha@) 5.0 Phthalocyanine Blue (SR-
1500 Sanyo Shikisha @) 15.01000.0 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 liquid with an MEQ of 60 was obtained.

A transparent electrode formed from 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, but the colored layer obtained was rough on the skin. This was a problem in practical use.

Comparative example 5 The following cation Tl@ bath was created.

Acrylic resin (made by Shinto Paint Co., Ltd.) 87.0 parts Ethyl cellosolve 43.5 Isopropyl alcohol 4.0 Acetic acid (neutralizing agent) 0.45 Ion exchange water 835.05 Tin oxide (T-1 made by Mitsubishi Metals Co., Ltd.) 10 .0 Silver (manufactured by Ultra Fine Particle Vacuum Metallurgy Co., Ltd.) 5.0 Phthalocyanine Green (manufactured by SAχ Sanyo Shiki Co., Ltd. 15.
01000.0 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 liquid with an MKQ of 10 was obtained, but this bath liquid did not contain aggregates of acrylic resin. The bath liquid was extremely unstable and unsuitable for practical use.

As specifically described in the examples above, the method for manufacturing a multicolor display device according to the present invention is simple and does not require special means such as resist dyeing to separate colors for multicolorization. color filters can be manufactured. Furthermore, the color filter is robust and free of pattern shift, and can achieve high display quality and reliability even when combined with display materials such as liquid crystal. Moreover, since the color filter is made conductive, it can be driven at a lower voltage with less drive voltage loss compared to conventional color filters, and the abrupt change in voltage-transmittance characteristics has been improved, allowing matrix drive. The present invention also provides a method for manufacturing a multicolor display device suitable for use in various applications.

[Brief explanation of drawings]

Fig. 1 is a sectional view of a conventional multicolor display device using a color filter, Fig. 2 is a sectional view of a multicolor display device manufactured by the manufacturing method of the present invention, and Figs. 3 shows voltage-transmittance characteristics of an example of the invention. 1.8-----One display device 2.9--One display electrode 3.10--One color filter 4.1.1--One counter electrode 5.12--One Counter substrate 7.14 --- Display material patent applicant Seiko Electronics Co., Ltd. Shinto Paint Co., Ltd. , Name of the invention Multi-color display device and its manufacturing method 3, Relationship with the person making the amendment 1'1 Particularly to the applicant 1hNbuta 5 Kusunoki 6 of the detailed description of the invention in the specification to be amended, Contents of the amendment (1) “rlo11ΩG” on page 2 of the specification, line 13
“ΩG” I corrected. (2) On page 8, line 3, insert "1" next to "electrodeposition composition." (3) Same @ page 8, lines 4 to 5, next to “in the electrodeposition bath” [
, insert J. (4) On page 8, line 8, insert "1," after "between". (5) Same No. 12 Tei No. 4? ``' in l-range'' is followed by ``
," is inserted. (6) Insert [-1] next to "within range" in line 6 of page 12. (r) Insert "1" next to "Organic pigments" at the end of page 15. (8) On page 18, line 3, ``Patent'' is corrected to ``Special note J.'' (9) On page 22, line 13, ``In an electrodeposition bath'' is corrected as ``In an electrodeposition bath.'' (10) Insert "," after "through spacer 13" on page 23, line 14 0 (11) Insert "phthalocyanine blue" in lines 4 and 5 of page 27 as "each pigment" I am corrected. (12 From the bottom of page 30 of the same page, insert ``contains'' in the 5th line "contains 0" and β2 0 (13) From the bottom of page 30 of the same page, insert ``contains'' before the 4th line "polynis i"le. Up

Claims (1)

[Scope of Claims] 1. In a multicolor display device using a multicolor color filter, a plurality of conductors [I A multicolor display device comprising a multicolor filter provided with a multicolor layer made of a polymer resin or an anionic polymer resin and having a resistivity of 10!2 Ωα or less. 2. The device according to claim 1, wherein the cationic polymer resin has a base number of 0.2 to 2 degrees. 3. In a method of manufacturing a multicolor display device using a multicolor filter, the multicolor filter is coated on a plurality of conductive layers arranged insulated from each other on a substrate, and coated with a cationic polymer resin electrodeposition liquid or a cationic polymer resin electrodeposition liquid. A colored layer having a specific resistance of IQ11Ωα or less is selectively formed by electrodeposition from an anionic polymer resin electrodeposition liquid, and the operation is then carried out using a cationic polymer resin electrodeposition liquid of a different color or an anionic polymer resin electrodeposition liquid of a different color. 1. A method for manufacturing a multicolor display device, characterized in that a multicolor layer is formed by repeated use of a molecular resin electrodeposition solution. 4. The base number of the cationic polymer resin is 0.2 to 2.0.
And Mll of electrodeposition liquid! The method according to claim 3, wherein the Q value is 15 to 50.