JPH043122A - Production of color display device - Google Patents

Abstract

PURPOSE:To simplify the process for production by patterning the photoresister itself on a substrate having a conductive layer, then forming colored layers by electrodeposition and repeating this process every multicolor. CONSTITUTION:The conductive layer 2 is formed on the substrate 1. A positive type photosensitive resin compsn. layer 3 is formed on the conductive layer 2. A mask 4 having prescribed patterns is mounted on this positive type photosensitive resin compsn. and the compsn. is exposed to allow the elusion of the photosensitive resin compsn. layer of the exposed parts. The exposed parts are then eluted by a prescribed eluting soln. to obtain the patterned substrate. Further, the conductive layer 2 is energized and the colored layer 5 and 6, 7 are formed by the electrodeposition in an electrodeposition bath. A transparent substrate 8 is pressed to the colored layers formed on the substrate to transfer the colored layers to the transparent substrate 8. The process is simplified in this way and the film functions are improved.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for manufacturing a colored display device having a colored layer formed by electrodeposition and transfer techniques.

[Prior Art] A method that is attracting attention in the manufacturing method of a colored display device is a method of forming a colored layer by electrodeposition.

JP-A No. 61-279803 discloses a method for manufacturing a color filter in which a transparent electrode is provided on a transparent substrate, a positive type photosensitive resin layer is exposed and developed, and a colored layer is formed by electrodeposition. There is. According to this method, the transparent electrode, which is also the driving electrode for the liquid crystal, must drive the liquid crystal through the colored layer, which is an insulator, and the driving voltage becomes extremely high. Therefore, at present, a transparent electrode layer for driving the liquid crystal is further provided on the colored layer formed based on the above method to ensure driving power. However, forming a variable electrode layer complicates the process and requires patterning of the transparent electrode, which is not economical. Furthermore, the light transmittance of a transparent electrode is actually 80 to 85%, and forming two layers means that the light transmittance is poor, which deteriorates the performance as a color display device. .

As a solution to the above-mentioned drawbacks, the present inventors have already proposed a method in which a colored layer is first formed on an original plate by electrodeposition, then transferred to a transfer substrate, and then transferred again to a transparent substrate (
(Japanese Unexamined Patent Publication No. 64-22379). In this case, when coloring in multiple colors, it is necessary to repeat the above operation on the necessary types of original plates. This method has the advantage that no electrode is present between the colored layer and the transparent substrate. The present inventors have made repeated studies to further improve this manufacturing method, simplify the process, and obtain a highly accurate colored display device.

[Problems to be Solved by the Invention] An object of the present invention is to provide an improved method for manufacturing a color display device.

[Means for Solving the Problem] The present inventors patterned the photoresist itself on a substrate having a conductive layer, then formed a colored layer by electrodeposition, and repeated this process for each color. , has been found to solve the above drawbacks.

That is, the present invention provides (a) providing a positive photosensitive resin layer on a conductive layer formed on a substrate, exposing the conductive layer in the portion to be colored in a predetermined color by exposing and developing, and (b) A colored layer is formed on the conductive layer by electrodeposition, (c) the remaining positive photosensitive resin layer is exposed and developed to expose a portion of the conductive layer to be colored in a color different from the colored portion, and (d) the colored layer is colored in a different color from the colored portion. Form colored layers of different colors on the exposed conductive layer by electrodeposition, (e) repeat steps (C) and (d) as necessary, and (f) deposit the obtained colored layer on a transparent substrate. Provided is a method for manufacturing a colored display device, which is characterized by transferring and fixing a color to a color display device.

The present invention will be explained based on the drawings.

Fig. 1 is a process diagram showing the steps of the manufacturing method of the present invention, Figs. This is a diagram seen from.

The manufacturing method of the present invention includes a step of patterning a photoresist on a substrate having a conductive layer as shown in Figures 1(a) to (d), and forming colored layers as shown in Figures 1(e) to (j) on the substrate. The process can be broadly divided into three steps: a step of forming a colored display device by a transfer method using the colored layers on the substrate shown in FIGS. 1(k) to 12(12).

First, as shown in FIG. 1(a), a conductive layer 2 is formed on a substrate l. The substrate 1 is made of a material such as glass or plastic. The conductive layer 2 is formed from a transparent conductive film made of copper or other conductive metal, tin oxide, indium oxide, or the like. The conductive layer 2 is formed by a method such as adhesion, plating, spraying, or sputtering. In terms of cost and other aspects, it is preferable to sputter copper onto a plastic substrate. Next, as shown in Figure 1(b),
A positive photosensitive resin composition layer 3 is formed on the conductive layer 2. The positive photosensitive resin composition may be one that dissolves in the exposed area or in the developing solution.
No. 1365, U.S. Pat. No. 1,762,033, U.S. Pat. No. 267
No. 9498 specification and rTAGA Proceed
ingsJ pages 241-244 (1967), A.
A photosensitive resin composition containing a diazonium salt and a barafaldehyde condensation product described in the paper of R.
Photosensitive resin compositions containing ortho-quinone diazides (or orthodiazooxides) described in the specifications of Japanese Patent Publication No. 3-28403 and Japanese Patent Publication No. 45-9610; 22085, British Patent No. 843541, photosensitive resin compositions containing alkali-soluble aphthopolymers,
Japanese Patent Publication No. 417100, Japanese Patent Publication No. 28725-1972, US Patent No. 2,692,826, Japanese Patent Publication No. 2208-1987
No. 2, a photosensitive resin composition containing an AND compound that can be developed with water or an alkaline aqueous solution, as described in each specification, etc.;
or JP-A-59-45439 and Japanese Patent Application No. 1987-
Examples include the photosensitive resin composition described in Japanese Patent No. 132126. In the present invention, it is necessary to perform exposure and development multiple times with the same positive photosensitive resin composition, and necessary measures for this purpose (for example, providing a protective layer so as not to be modified by a developer) can be taken. Some of the photosensitive resin compositions described above do not require such means.

A mask 4 having a predetermined pattern is placed on the positive photosensitive resin composition 3 (FIG. 1(C)), and exposed to light so that the exposed portions of the photosensitive resin composition layer can be eluted,
Next, a patterned substrate is obtained by elution with a predetermined eluent (FIG. 1(d)). Masks and elution techniques are well known.

As shown in FIG. 1(A), this substrate has a conductive layer 2 exposed in the areas where coloring is required.

As shown in FIG. 1(e), a colored layer (for example, red (R) 5) is formed by applying electricity to the conductive layer 2 and depositing it in an electrodeposition bath. ) as shown in the figure.

The synthetic polymer resin used as a film-forming component of the electrodeposition bath used in this production method may be cationic, anionic, or amphoteric, and may be of various conventionally known types, such as acrylic resins, epoxy resins, Examples include urethane resin, polybutadiene resin, polyamide resin, carboxyl group-introduced polybutadiene, and carboxyl group-introduced alkyd resin. Note that, depending on the ionicity of the synthetic polymer resin, some may attack the conductive layer 2, and it is necessary to take this point into consideration when selecting film-forming components. For example, if the conductive layer 2 is metal,
If the film-forming component is anionic, electrode elution may occur, which is not appropriate. Moreover, in the case of a transparent conductive film, it is not preferable that the film is cationic. Detailed information on the electrodeposition bath and other details can be found in Japanese Patent Application Laid-open No. 114592/1982 and Japanese Patent Application No. 1983 filed by the present inventors.
2i6321 etc. in detail.

This electrodeposition coating material may be either photocurable or thermosetting.

Next, as shown in FIG. 1(f), a positive mask 4 is placed on the colored layer and positive photosensitive resin layer formed on the substrate 1 (FIG. 1(f)), and exposed to light in the same manner as above. The exposed portion of the photosensitive resin composition layer is eluted to obtain a patterned substrate (FIG. 1(g)). Looking at this from a plane, the first (
C) It becomes like the figure.

Furthermore, as shown in FIG. 1(h), a colored layer (for example, green (G) 6 is formed by applying electricity to the conductive layer 2 in an electrodeposition bath. It becomes like (d).

Next, for the third color, a colored layer (for example, blue (B)) 7 is formed by repeating the steps in FIGS. 1(f) to (h). When viewed from a plane, it looks like Figure 1 (E).

The substrate on which the colored layers (R, G, B) and the positive photosensitive resin layer are mounted is fully exposed to light, and the colored layers (R, G, B) are further eluted.
G, B) exposing conductive layers 2 other than (first (j)
figure). If you look at this from a plane, it will look like the first picture).

Next, as shown in FIG. 1(k), a transparent substrate 8 is pressed against the colored layer formed on the substrate 1 (FIG. 1(k)).
As shown in FIG. 1(a) or FIG. 1(g), a colored layer is transferred onto a transparent substrate 8. The transferred substrate 1 is reused in the process shown in FIG. 1(b).

The transfer may be performed using a rubber-coated roller so that the surface of the colored layer 5.6.7 comes into contact with the surface of the transparent substrate 8. If the electrodeposition layer is photopolymerizable, after exposure treatment, the substrate 1
may be separated. Exposure is usually 200m at room temperature in air.
J/cm" will cure, but if you want to increase the fastness of the colored layer, you can increase the irradiation dose. Also, if the electrodeposited layer is thermosetting, after separating the substrate l, It may be hardened by heat treatment.

A transparent electrode is formed on the transparent substrate 8 on which the colored layer is formed by a method such as vapor deposition or sputtering, and is used as a colored display device.

(Example) The present invention will be explained in more detail with reference to Examples. The present invention is not limited to these examples.

Reference Example 1 "Preparation of positive photosensitive resin composition" Tertiary butyl acrylate 15.0?, 15.0@ tertiary butyl acrylate, 15.0@ and methyl methanolate 2
0.0 g was added, and the mixture was heated and stirred at 60°C for 10 hours in a nitrogen stream. After cooling, the reaction product was diluted with tetrahydrofuran and washed with petroleum ether/methanol. The polymer had a number average molecular weight of 42.59 (yield 85.0%) and (
GPC) was 51°000. This polymer was dissolved in tetrahydrofuran so that the solid content was 20% by weight, and 10% by weight of triphenylsulfonium hexafluoroantimonate was added to the polymer to obtain a positive photosensitive resin composition. .

Reference Example 2 "Preparation of a cationic photosensitive electrodeposition resin composition for forming a color filter" Blue Green Red Phthalocyanine Blue Phthalocyanine Green -5,0 Azo metal salt red pigment 5.0 1000, 01000.01000.ON, N- An organic polymer obtained by copolymerizing a compound obtained by equimolar reaction of diethylamine ethyl methacrylate, styrene, ethyl acrylate, and p-hydroxybenzoic acid with glycine acrylate at a molar ratio of 3:2:4.1 and a weight average molecular weight of 70,000. A cationic photosensitive resin composition consisting of 1 part by weight of the combined binder go@, 05 parts by weight of 2.2-dimethoxy/2-phenylacetophenone, and 14.5 parts by weight of to9methylolpropane triacrylate was diluted with ethylene glycol monobutyl ether to reduce the volatile content to 80 parts by weight. %, neutralized with 0.5 equivalent of acetic acid, and adjusted to 10% volatile content with pure water.

Three colors of cationic electrodeposition bath liquids were prepared by blending the following pigments into the electrodeposition resin composition prepared as described above.

Example 1 The positive photosensitive resin composition of Reference Example 1 was applied onto the polyimide film on which the copper foil 2 was placed using a spinner, and dried to form the positive photosensitive resin composition layer 3 on the copper foil. did.

Next, it was exposed to light using a high-pressure mercury lamp through a mask having a predetermined pattern, and when this was developed with an alkaline aqueous solution, salt was formed and eluted in the exposed area, and the surface of the copper layer 2 was exposed. Next, the substrate 1 with exposed copper@2 was immersed in the electrodeposition bath of the red cationic photosensitive electrodeposition resin composition prepared as described above, and a DC voltage of 10 volts was applied to the copper layer as a negative electrode. It was applied for a minute.

Thereafter, the substrate was pulled up and thoroughly washed with water. At this time, the electrodeposited resin composition does not adhere to the positive photosensitive resin composition on the copper layer and is washed away with water, but the polymer that adheres to the electrode to which voltage is applied is insoluble in water. Because of this, it cannot be washed away with water. After washing with water and drying, a highly transparent colored polymer film is formed on the electrode.

Next, this substrate was exposed to light using a high-pressure mercury lamp through a mask 4 with a shifted pattern, and further developed with an alkaline aqueous solution, so that the surface of the copper layer 2 was similarly exposed.

Next, the substrate 1 on which the red colored layer with the copper layer 2 exposed was immersed in the electrodeposition bath of the green cationic photosensitive electrodeposition resin composition described above, and the IOV was applied using the copper electrode as the negative electrode. A DC voltage was applied for 1 minute, and then the substrate was pulled up and thoroughly washed with water. At this time, the green electrodeposition composition does not adhere to the positive photosensitive resin composition on the copper layer and the red colored layer, but is washed away by water washing. After washing with water and drying, a highly transparent green polymer film is formed.

Furthermore, a mask 4 with a shifted pattern is exposed and developed on this substrate in the same manner, and blue electrodeposition is applied for 1 minute at a DC voltage of 1OV. After washing with water and drying, a blue polymer film is similarly formed.

The remaining positive photosensitive resin composition and the substrate 1 on which the colored layers of red, green, and blue have been formed are exposed on the entire surface with a high-pressure mercury lamp and developed with an alkaline aqueous solution, leaving the colored layers and forming the positive photosensitive resin composition. The material was eluted and the surface of the copper layer 2 was exposed.

Next, red, green, and blue patterns 5 are formed on the substrate.
．． The surface of 6.7 is in contact with the glass substrate which is the transparent substrate 8, and the entire surface is heated with 200 mJ from the glass substrate using a high pressure mercury lamp.
/cm' exposure, and then the colored layer was transferred by peeling.

The thickness of the colored layer was 2.0 microns.

(Effects of the Invention) The color filter obtained by the manufacturing method of the present invention has high reliability even if it has a fine pattern, and an excellent color display device can be obtained. According to the conventional method, a 100-color layer is formed on a transparent electrode by a combination of resist and electrodeposition, but this method has the problems of complicating the process and reducing light transmittance. Furthermore, by a combination of resist and electrodeposition, the image is first transferred to a transfer substrate and then transferred again to a transparent substrate, but in this case as well, there are limits to the complexity of the process and the repeated use of the material.

According to the present invention, there is no need for transparent electrodes or repeated transfer, and it is possible to simplify the process and improve the film function.

Furthermore, since a colored layer is formed by electrodeposition in the gaps between the photosensitive resin layers and transferred, the colored layer maintains a flat and sharp shape and has good color clarity.

[Brief explanation of the drawing]

FIG. 1 is a process diagram showing the steps of the manufacturing method of the present invention, and FIGS. 1(a) to (12) are cross-sectional views.
Figures a) to (g) are views seen from a plane. In the figure, 1... substrate, 2... conductive layer, 3... photosensitive resin composition, 4 fat mask, 5... first color colored layer, 6...
, second colored layer, 7... third colored layer, 8... transparent substrate. Patent Applicant Nippon Paint Co., Ltd. Agent Patent Attorney Said Ao (and 2 others) Figure 1 (Zo/2) Figure 1 (Ki No. 1) Ii Haya l =

Claims (1)

[Claims] 1. (a) A positive photosensitive resin layer is provided on a conductive layer formed on a substrate, and exposed and developed to expose a portion of the conductive layer to be colored in a predetermined color; (b) ) forming a colored layer on the exposed conductive layer by electrodeposition; (c) exposing and developing the remaining positive photosensitive resin layer to expose a portion of the conductive layer to be colored in a color different from the colored portion; ( d) forming colored layers of different colors on the exposed conductive layer by electrodeposition; (e) repeating steps (c) and (d) as necessary;
(f) A method for producing a colored display device, which comprises transferring and fixing the obtained colored layer onto a transparent substrate.