JPH08292314A - Electrodeposition coating material composition for forming color filter and production of colored layer of color filter using the composition - Google Patents

Abstract

PURPOSE: To obviate the occurrence of partial dissolving or peeling of colored layers from substrates in spite of execution of repetitive exposing and developing stages and to make it possible to form color filters having good heat resistance and light resistance by incorporating a resin mixture contg. a high-polymer resin having an ionic group and having water solubility or water dispersibility and a compd. having a hydroxyl group and siloxane skeleton in the molecule and coloring agents into the above compsn. CONSTITUTION: This electrodeposition coating material compsn. contains the resin mixture contg. the high-polymer resin having the ionic group and having the water solubility or water dispersibility and the compd. having the hydroxyl group and siloxane skeleton in the molecule at a ratio of 30:70 to 99:1 by solid content and the coloring agents. The compd. having the siloxane skeleton is expressed by the formula. In the formula, R<1> is methyl; 3-hydroxy propyl, etc.; R<2> and R<3> are independently methyl, phenyl, etc.; R<4> is methyl, phenyl, etc.; R<5> is methyl, phenyl, etc. One of R<1> , R3 is selected so as to be a terminal hydroxyl group; l is an integer from 2 to 4; (m) is an integer from 1 to 30; (n) is an integer from 0 to 2.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a color filter forming technique used for various display devices such as liquid crystal display devices, and more particularly to electrodeposition which can be suitably used for forming a color filter colored layer by an electrodeposition method. The present invention relates to a coating composition and a method for producing a color filter colored layer using the same.

[0002]

2. Description of the Related Art In recent years, a liquid crystal display (LCD) has attracted the most attention among all flat panel displays, and is expected as a high-definition color display that is opposed to a cathode ray tube (CRT).

Among the liquid crystal displays, a color filter is an important member for colorization. Currently used color filter manufacturing methods include dyeing method, printing method, pigment dispersion method, electrodeposition method, etc., all of which are excellent methods, but large screens, high definition, and low cost There remains a problem to be solved in terms of manufacturing technology. For example, in the case of the dyeing method, it is necessary to apply a dye-proof coating and a precision photolithography process to prevent co-dyeing each time the color is changed, and the process is complicated. In the case of the printing method, there is a limit to the miniaturization of the pattern and there is a problem in dimensional accuracy. Further, in the case of the pigment dispersion method, it is generally necessary to apply a colored resist by a spinner or the like every time the color is changed, and then repeat the precision photolithography process, which is not only complicated but also expensive at the time of spinner application. The problem is the low coating efficiency of various materials. In addition, an oxygen blocking film may be required each time the colored resist is applied, which further complicates the process.

Regarding the method of manufacturing a color filter by the electrodeposition method, two kinds of methods have been developed and mass production has been achieved. The first method is to form a transparent electrode by patterning a transparent conductive film previously formed on a substrate into a desired shape as described in JP-A-59-114572, and then to form a colored layer of the same color. In the colored electrodeposition coating solution bath, a voltage is selectively applied to the portions to be formed to form colored layers, which are repeated for a desired number of colors. This manufacturing method first requires patterning of the transparent electrode and requires extremely careful handling so as to prevent disconnection of patterns and short circuit between patterns. Further, the shape and arrangement of the colored layers are determined by the shape and arrangement of the electrode pattern thereunder, and the shape and arrangement of each colored layer are limited, and the degree of freedom is restricted.

On the other hand, the second method is JP-A-61-2.
No. 03403, No. 61-272720, and using a positive photosensitive resin composition on a substrate having a transparent conductive layer, exposing a desired portion (a portion to be a colored layer of the same color), The opening of the resin composition film is formed by development to expose the underlying transparent conductive film, the substrate is immersed in a colored electrodeposition coating solution bath, and then a current is applied to form a colored layer. This method is capable of producing a color filter in which each colored layer has a desired shape and arrangement by repeating exposure, development and electrodeposition for the required number of colors. This second
There is no restriction on the pattern shape and arrangement of each colored layer,
High-definition patterning is possible, and the film thickness can be easily controlled depending on the electrodeposition conditions, and a large screen can be achieved with a uniform film thickness. Further, the coating efficiency is high and the electrodeposition process can be easily automated, and the manufacturing cost can be reduced.

Generally, an electrodeposition coating composition has a coloring agent comprising a resin component, a pigment or a dye, which has an anionic or cationic ionic group, and the group is partially neutralized with a counter ion. It is used by adding a curing agent, a solvent and the like in the state of an aqueous solution or an aqueous dispersion. Regardless of the ionic property, the coating film immediately after electrodeposition contains water, a solvent, etc. and has poor smoothness, and a uniform film is obtained by heating and drying. For forming a color filter, an anionic electrodeposition coating material is preferably used in terms of film characteristics. In this case, the alkali resistance of the deposited film is inferior due to simple drying, that is, heat treatment to achieve removal of water, solvent and smoothing of the film surface, and repeated contact with the alkaline developer of the exposed portion of the positive photosensitive resin composition. This causes the film to swell or peel. Therefore, in order to impart resistance to the alkali developing solution, heat treatment to reach thermosetting, usually 150 ° C. or higher, is required. However, when a photosensitive resin composition using a general quinonediazide compound as a positive type is used, thermal decomposition of the photosensitive group occurs in this temperature range, making repeated exposure and development (so-called sequential exposure development) difficult. Further, when the surface of the unexposed portion of the photosensitive resin composition comes into contact with an alkali developing solution or an electrodeposition coating, it may deteriorate in quality and the exposure and development treatment may not be possible again, resulting in unstable performance.

On the other hand, the present applicant has proposed a method for forming a color filter using a positive type photosensitive resin composition instead of a quinonediazide compound (JP-A-4-2474).
No. 02). Although this method can suppress the deterioration of the sequential exposure developability due to contact with the developing solution, electrodeposition coating, etc., which is observed when a quinonediazide compound is used, heat treatment should impart resistance to the alkaline developing solution to the electrodeposition film. It is not sufficient to satisfy both the requirement of suppressing thermal deterioration of the photosensitive material and ensuring the sequential exposure and developability. That is, if a heat treatment condition of a relatively short time is adopted in order to secure the sequential exposure and developability, the alkali resistance of the electrodeposition film formed by electrodeposition in advance is insufficient, and it is partially dissolved by the development after the exposure in the next step. The film thickness may be reduced or peeling may occur.

Further, the color filter using the current colored electrodeposition coating composition by the electrodeposition method does not satisfy the market demand for heat resistance in a high temperature baking step of 200 ° C. or higher and light resistance when formed into a panel. No improvement is desired.

[0009]

In contrast to the above problems, the present invention provides a color filter which exhibits sufficient water resistance at the time of development even by short-time heat treatment, has a small change in chromaticity during high temperature baking, and is excellent in light resistance. And a method for producing a color filter colored layer using the same.

[0010]

According to the present invention, a polymer resin having an ionic group and having water solubility or water dispersibility and a compound having a hydroxyl group and a siloxane skeleton in the molecule are contained in a solid content ratio. An electrodeposition coating composition for forming a color filter, which comprises a resin mixture contained in a ratio of 30:70 to 99: 1 and a colorant is used. By using this coating composition, in addition to the characteristics of the conventional electrodeposition method,
It is possible to form a color filter having good heat resistance and light resistance without the electrodeposited colored layer being partially dissolved or peeled from the substrate even after repeated exposure and development steps.

The water-soluble or water-dispersible polymer resin having an ionic group used in the present invention usually has a base having an acidic group such as a carboxyl group in the resin skeleton (eg organic amine, ammonia). It may be one that is water-soluble or water-dispersed by being neutralized with and is negatively (-) charged, and the object to be coated serves as an anode (anionic) during electrodeposition coating. Alternatively, the resin skeleton has a basic group such as an amino group and is neutralized with an acid (for example, an organic acid) to be water-soluble or water-dispersed to be positively (+) charged and to be coated during electrodeposition coating. May be used as a cathode (cationic).

These resins are various conventionally known resins, for example, Oil Chemistry, Vol. 34, No. 2, pp. 1-11 (1985).
As mentioned above, acrylic resins, epoxy resins, polybutadiene resins, alkyd resins, polyester resins and the like can be mentioned. Among them, anionic acrylic resin having an acid group can be preferably used.

The anionic acrylic resin having an acid group is
An unsaturated monomer having an acid group (1 to 80 wt%) and another unsaturated monomer (20 to 99 wt%) copolymerizable with the unsaturated monomer having an acid group are conventionally known. It can be easily produced by copolymerization according to the method. The acid group is preferably a carboxyl group, and known unsaturated monomers having an acid group may be used. For example, acrylic acid, methacrylic acid, itaconic acid, fumaric acid, maleic acid, maleic anhydride, or derivatives thereof such as ω-carboxy-polycaprolactone monoacrylate, phthalic acid monohydroxyethyl acrylate, acrylic acid dimer, and JP-A-62-62. -161742 and 63-
Examples thereof include reactive acrylic monomers having a carboxyl group described in JP-A-137913. These may be used alone or in combination.

A known unsaturated monomer having a hydroxyl group is preferably used as one of the other unsaturated monomers copolymerizable with the above-mentioned unsaturated monomer having an acid group. It The hydroxyl group-containing unsaturated monomer is used in a range of 0 to 50 wt% as necessary, and examples thereof include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, 4-hydroxybutyl acrylate. , 4-hydroxybutyl methacrylate, lactone-modified hydroxyethyl acrylate, lactone-modified hydroxyethyl methacrylate, or derivatives thereof.

As the other unsaturated monomer which can be copolymerized with the above-mentioned unsaturated monomer having an acid group, a conventionally known thermal cross-linking agent such as methylol acrylamide compound and N-methylol alkyl ether acrylamide compound can be used. A polyunsaturated monomer is also preferably used. These are used in a range of 0 to 45 wt% as necessary, and include, for example, N-methylol acrylamide, N-methylol methacrylamide, N-methoxymethyl acrylamide, N-methoxymethyl methacrylamide, N- (n-butoxy) methyl. Acrylamide, N- (n-butoxy) methylmethacrylamide,
Examples thereof include N- (isobutoxy) methylacrylamide, N- (isobutoxy) methylmethacrylamide, and methylacrylamide glycolate methyl ether.

As the other copolymerizable unsaturated monomer, those known in the art can be used. Some of these are exemplified by methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate and isopropyl acrylate. , Isopropyl methacrylate,
n-butyl acrylate, n-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, t
-Butyl acrylate, t-butyl methacrylate, n-
Hexyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, lauryl acrylate, lauryl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, styrene,
Examples include α-methylstyrene, vinyltoluene, vinyl acetate, acrylonitrile and the like. These are used alone or in combination to obtain desired resin properties such as Tg and solubility (SP).

The acrylic resin composition has a number average molecular weight of 500 to 100,000, more preferably 1,000.
Within the range of 50,000. When it is less than 500, it is difficult to develop alkali resistance and solvent resistance of the colored layer even after heat curing. On the other hand, when it exceeds 100,000, the thermal fluidity is remarkably reduced and the colored layer is not treated by heat treatment. Becomes difficult to flatten. The acrylic resin may be used alone or as a mixture with another polymer resin having an ionic group.

The compound having a siloxane skeleton used in the present invention is specifically represented by the following general formula (I):

[0019]

[Chemical 4]

(Wherein R ¹ is a methyl, 3-hydroxypropyl or 3- (hydroxyethoxy) propyl group,
R ² and R ³ are independently a methyl, phenyl, phenylethyl, 3-hydroxypropyl, or 3- (hydroxyethoxy) propyl group, R ⁴ is a methyl, phenyl, or phenylethyl group, and R ⁵ is It is a methyl, phenyl, phenylethyl, or isobutyl group, and at least one of R ¹ and R ³ is selected to be a terminal hydroxyl group, l is an integer of 2 to 4, and m is 1 to Thirty
Is an integer of 0, and n is an integer of 0 to 2).

The compound having a siloxane skeleton has good compatibility with the above-mentioned polymer resin having an ionic group, and also has a hydroxyl group in the molecule, so that it is a curing agent during heat treatment of the electrodeposition film. Etc. to easily react to form a uniform coating film and impart the chemical resistance, heat resistance, light resistance and insulating property of the silicone compound. On the other hand, when there is no reactive group or when a poorly compatible silicone compound is used, these compounds migrate to the surface of the coating film to form a silicone liquid film, which may cause pinholes due to repellency, poor adhesion, or insufficient curing. Problems such as deterioration of chemical resistance are likely to occur. Further, when it is chemically extremely stable and is present in water as an electrodeposition coating composition, deterioration due to hydrolysis is not observed, and therefore the storage stability of the electrodeposition liquid is good and electrodeposition for obtaining a predetermined film thickness is achieved. No change in the conditions or the characteristics of the deposited film was observed over the long term.

A method for producing a compound having a hydroxyl group and a siloxane skeleton is described on pages 29-30 of the Symposium on Silicon Materials Chemistry, 1990. Several of these are commercially available and are industrially available. If the following compounds are exemplified, the following may be mentioned (wherein
Me is a methyl group, Ph is a phenyl group, iBu is an isobutyl group, and A represents a 3- (hydroxyethoxy) propyl group):

[0023]

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[0024]

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[0025]

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[0026]

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[0027]

[Chemical 9]

[0028]

[Chemical 10]

[0029]

[Chemical 11]

[0030]

[Chemical 12]

[0031]

[Chemical 13]

[0032]

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The amount of hydroxyl groups in these compounds having a siloxane skeleton may be at least one on average in one molecule, but from the viewpoint of thermosetting property, it is preferably at least three.

After the compound having a hydroxyl group-containing siloxane skeleton and the above-mentioned polymer resin having an ionic group are mixed with a desired thermosetting agent or additive in the presence of an organic solvent, the ionic group species is treated. It can be made water-soluble or water-dispersed by adding deionized water after neutralizing with a compound serving as a counter ion. At this time, the amount of the ionic groups in the solid content of the polymer resin is in the range of 0.1 to 5.0 equivalents / kg, and more preferably in the range of 0.2 to 3.5 equivalents / kg, When it is less than 0.1, it is difficult to obtain a stable dispersion in water even by neutralization with an excessive amount of counterion. On the other hand, when it is more than 5.0, the amount of ionic groups is too large and sufficient. Water resistance of the final coating film becomes insufficient even by such thermal curing. Further, the amount of counterion is preferably an amount corresponding to a neutralization rate of 20 to 120% with respect to the ionic group. That is, when it is less than 20%, it is difficult to obtain a stable dispersion in water, and when it is more than 120%, excessive counter ions deteriorate the electrodeposition characteristics.

The polymer resin having an ionic group and the compound having a hydroxyl group and a siloxane skeleton have a solid content ratio of 30: 7.
The mixture is used in the range of 0 to 99: 1, more preferably 50:50 to 98: 2. When the resin having an ionic group is 30 wt% or less, the water dispersion stability cannot be secured,
On the other hand, when it exceeds 99 wt%, the effect of mixing the compound having a siloxane skeleton is not exhibited. As the thermosetting agent, a conventionally known one such as a melamine compound or a blocked isocyanate compound is added in an amount of 0 to 50 parts by weight based on 100 parts by weight of the resin solid content which is usually mixed. It is not particularly necessary when a self-crosslinking reactive group is introduced into the resin skeleton having an ionic group by copolymerization of the above-mentioned N-methylolalkyl etherified acrylamide or the like. If necessary, a dye, a pigment, a heat curing accelerator, etc. may be contained in the resin mixture before being dispersed in water.

Further, the electrodeposition coating composition in the present invention is
In addition to the water-solubilized or water-dispersible resin mixture,
Further, it contains a colorant component such as a dye or pigment of a desired color. The colorant may be any conventionally known one, such as monoazo, disazo, insoluble azo such as metal complex, azo lake, phthalocyanine, anthraquinone, thioindigo, perylene, perinone, quinacridone, isoindo. Various organic pigments such as linone-based, isoindoline-based, dioxazine-based, quinophthalone-based, diketopyrrolopyrrole-based and inorganic pigments such as carbon black and titanium black are often used in terms of heat resistance and light resistance. These may be used after being mixed by mixing to obtain a desired color tone. The colorant may be water-dispersed in a state of being contained in the resin mixed solution in advance as described above, but when the content of the colorant is large, the problem that the water dispersion stability is deteriorated easily occurs. The amount of the coloring agent necessary for imparting a coloring concentration to the electrodeposition deposited film is dispersed in water by using a polymer resin dispersant having an ionic group in advance, or a surfactant is used in combination, and the above-mentioned water-solubilization or water The method of mixing with the dispersed resin mixture is preferable. in this case,
The polymer resin containing an ionic group mixed with a compound having a hydroxyl group and a siloxane skeleton has the same ionicity (anionic or cationic) and the polymer dispersant in which the colorant is dispersed. The species do not necessarily have to be the same.

An example of a method for producing a color filter colored layer using the electrodeposition coating composition according to the present invention will be described. First of all
The method of (a) comprises a step of (a) forming a photosensitive resin film on a substrate having a transparent conductive layer on the surface thereof, and (b) having a pattern corresponding to a desired colored layer site on the photosensitive resin film. Exposing through a mask and then developing to provide a resist opening corresponding to a desired pattern to expose a part of the transparent conductive layer; and (c) a colored layer having a desired color on the site by an electrodeposition method. And a step for forming a color filter colored layer for a multicolor display device by repeating steps (b) to (c) a required number of times.

The above method will be described in more detail. First, as shown in FIG. 1A, the transparent conductive layer 2 is formed on the substrate 1. As the substrate 1, any substrate generally used in a multicolor display device may be used, and a glass substrate, a plastic substrate or the like can be used. For the transparent conductive layer, a material containing tin oxide, indium oxide, antimony oxide, or the like as a main component is preferably used. The method for forming the transparent conductive layer is not particularly limited, and examples thereof include a spray method and a CVD method.
Known methods such as a method, a sputtering method, and a vacuum deposition method can be used.

Next, as shown in FIG. 1B, a photosensitive resin composition layer 3 is formed on the conductive layer 2 on the substrate 1. The photosensitive resin composition used at this time may be either a positive type (photosolubilizing type) or a negative type (photocuring type) as long as it has the above-mentioned sequential exposure and developability, but this production In the method, the positive type chemically amplified resist described in JP-A-6-3826 is preferably used (in the following description, the case of using this photosensitive resin composition will be described). The method for forming the resin composition layer is not particularly limited, but known methods such as a dipping method, a spray method, a roll coating method, a screen printing method, a spin coating method and an electrodeposition method can be mentioned.

A mask 4 having a predetermined pattern is placed on the photosensitive resin composition layer 3 (FIG. 1 (C)) and exposed.
Then, after heating if necessary, development is performed with an alkaline solution to open the photosensitive resin layer in a desired colored pixel portion to expose the underlying transparent conductive layer (FIG. 1D).
The mask and developing technique are known.

Then, as shown in FIG. 1 (E), a colored film is formed by passing current through the conductive layer 2 in the bath of the electrodeposition coating composition composition containing the desired colorant (for example, red (R)). ). The thickness of the coating film is controlled by setting the applied voltage and the applied time. After that, a uniform and smooth film is obtained by washing with water and drying by heating. At this time, heat drying is usually 50
It is carried out at 200 ° C., preferably 100 to 160 ° C. and 5 to 60 minutes. When the temperature is lower than 50 ° C. and the drying time is short, unnecessary components such as water and solvent in the electrodeposited film are not sufficiently removed, and it is difficult to obtain smoothness of the film. Meanwhile, 20
If it exceeds 0 ° C., the photosensitivity is remarkably lowered due to thermal alteration of the remaining photosensitive resin film, and the successive exposure and developability is lost.

Generally, a color filter used in a multi-color display device requires three colored layers of red (R), green (G), and blue (B). Therefore, after heating and drying the first color, It is necessary to form another second colored layer, and a colored layer corresponding to the second color (for example, green (G)) is exposed through a mask having a predetermined pattern, developed, and electrodeposited. (Figure 1
(F)-(H)). Similarly, the third color (for example, blue)
(B)) is also formed (FIGS. 1 (I) to (K)).

In addition to these colored layers, a black matrix may be formed if necessary. In that case, a desired portion to be colored was exposed through a mask to the substrate on which the colored layers (R, G, B) and the photosensitive resin coating remained (or, if a black colored layer was provided on the entire surface, the entire surface was exposed without a mask). After that, a black colored layer (black matrix) can be formed by development and electrodeposition in the same manner as in the above steps (FIGS. (L) to (M)). After that, generally, a baking step at 150 to 300 ° C. is performed to achieve sufficient thermosetting to obtain a colored layer having excellent chemical resistance, heat resistance, and light resistance.

In the above manufacturing method, the order of forming the colored layers is not limited to the order described above, and may be, for example, black, blue, green and red. The black matrix layer is formed not by the electrodeposition method but by a conventionally known method such as a printing method, a forming method using a colored resist, or a method of forming a chrome layer by a sputtering method in advance and processing it into a desired shape. Good.

In the formation of the colored layer by the electrodeposition coating composition of the present invention, any photosensitive material can be prepared by the following manufacturing method, apart from the manufacturing method using the photosensitive resin composition capable of sequential exposure and development described above. It can also be used for a hydrophilic resin composition.

That is, (a) a step of forming a photosensitive resin film on a substrate having a transparent conductive layer on its surface, (b)
A step of exposing a part of the transparent conductive layer by exposing on the photosensitive resin film through a mask having a pattern corresponding to a desired colored layer site and then developing to provide a resist opening corresponding to the desired pattern. , (C) a step of forming a colored layer of a desired color on the site by an electrodeposition method, and (d) a step of peeling off an unnecessary photosensitive resin film, and the steps (a) to (d) are performed as many times as necessary. This is a method for repeatedly producing a color filter colored layer.

The difference between this method and the above-mentioned method is that the photosensitive resin composition does not require sequential exposure, and any known photosensitive resin composition may be used.
The steps (a) to (c) may be carried out in the same manner as in the above-mentioned method, that is, after forming the opening of the photosensitive resin composition layer at the desired colored layer forming site, electrodeposition and heat drying. To form a uniform colored layer (FIGS. 2A to 2E).

As a method for peeling off the remaining photosensitive resin composition layer, a conventionally known method, for example, immersion in a peeling solution,
It is easily carried out by brushing, spraying a stripping solution, etc. (FIG. 2 (F)).

Also in this method, by repeating the steps (a) to (d), the second step is performed in the same manner as the above-mentioned method.
Colored and third colored layers can be formed (FIG. 2 (G)).
~ (O)). Further, in the same manner as the above-mentioned method, a black matrix may be formed, if necessary, in addition to the colored layer (FIGS. 2 (P) to (Q)).

Also in the above-mentioned manufacturing method, a stripping agent (generally an alkaline solution, an acidic solution, an organic solvent, etc.) is used in the stripping step.
On the other hand, it is necessary for the colored layer to have sufficient resistance, and the electrodeposition coating composition of the present invention is also useful for this purpose.

Further, the electrodeposition coating composition according to the present invention forms a colored layer through an electrically conductive underlying conductive film,
As long as electrical conduction is ensured in the underlying conductive film, it may have any shape or a pattern in which a part of the conductive film is removed by partial etching or the like.

[0052]

EXAMPLES The present invention will be described in more detail by way of examples. However, the present invention is not limited to these examples. In the following examples, parts indicate parts by weight.

Reference Example 1 Synthesis Example of Polymer Resin Having Ionic Group 270 parts of butyl propylene glycol was placed in a 1 liter separable flask equipped with a stirrer, a thermometer, a reflux condenser, a nitrogen inlet tube and a dropping funnel. After charging and raising the internal temperature to 120 ° C, styrene 17 was added under nitrogen.
2.8 parts, methyl methacrylate 141 parts, lauryl methacrylate 120 parts, 4-hydroxybutyl methacrylate 125.7 parts, methacrylic acid 40.5 parts and t-butyl peroxy-2-ethylhexanoate 16.8 parts are mixed. The resulting solution was added dropwise over 3 hours, and after 30 minutes at the same temperature, a mixed solution of 39 parts of butylpropylene glycol and 2.2 parts of t-butylperoxy-2-ethylhexanoate was added over 30 minutes. Then, the temperature was maintained for 90 minutes to obtain an anionic acrylic resin. The amount of acid groups in this resin was 0.78 equivalent / kg with respect to the resin solid content, and the number average molecular weight was 10,000.

Reference Example 2 Synthesis Example of Polymer Resin Having Ionic Group 320 parts of propyl propylene glycol were charged in the same reaction apparatus as in Reference Example 1, the internal temperature was raised to 85 ° C., and then methyl was introduced under nitrogen introduction. A mixed solution of 164 parts of methacrylate, 132 parts of n-butyl acrylate, 40 parts of 2-hydroxyethyl methacrylate, 24 parts of acrylic acid, 40 parts of N-methoxymethylacrylamide and 88 parts of propyl propylene glycol and 2,2'-azobis (2, 4-dimethyl valeronitrile) 12 parts of a mixed solution was dropped at the same time over 3 hours,
After 30 minutes at the same temperature, propyl propylene glycol 4
Parts and 2,2'-azobis (2,4-dimethylvaleronitrile) 0.4
Part of the mixed solution was added dropwise over 30 minutes, and then the same temperature was maintained for 90 minutes to obtain an anionic acrylic resin. The amount of acid groups in this resin is 0.83 equivalent / solid resin portion /
It was kg, and the number average molecular weight was 9,600.

Reference Example 3 Preparation of Positive Photosensitive Resin Composition 149 parts of propylene glycol monomethyl ether acetate was charged in the same reaction apparatus as in Reference Example 1, the internal temperature was raised to 85 ° C., and then t was introduced under nitrogen. -2 parts of a mixed solution of 80 parts of butyl methacrylate, 10 parts of methacrylic acid, 10 parts of diethylene glycol monoethyl ether acrylate and 1 part of t-butylperoxy-2-ethylhexanoate.
A polymer was obtained by dropping over a period of time and maintaining the same temperature for 4 hours. The acid value of this polymer was 68 and the number average molecular weight was 20,000. After cooling the reaction solution, propylene glycol monomethyl ether acetate 250
Parts and 15 parts of triphenylsulfonium hexafluoroantimonate were added to obtain a positive photosensitive resin composition solution.

Reference Example 4 Preparation of Colorant Dispersion SMA-1440A (styrene ester maleic acid copolymer partially esterified product, acid value 18) was added to deionized water 263.4 parts.
5, number average molecular weight 2500, manufactured by Monsanto) 100
Parts and 36.6 parts of triethylamine were added and stirred for 3 hours to obtain a polymer dispersant solution for pigment dispersion.

Then, after mixing 20 parts of this polymer dispersion and 55 parts of deionized water with 25 parts of each pigment shown in Table 1 below, a tabletop batch type SG mill (manufactured by Ohira System Co., Ltd.)
Each color dispersion was obtained by dispersing glass beads for 10 hours.

[0058]

[Table 1]

Example 1 Anionic acrylic resin 615.4 shown in Reference Example 1
Parts, 50 parts of the compound (i) having the siloxane resin skeleton described above, and hexamethoxymethylated melamine 5
After mixing 0 parts and 15.5 parts of triethylamine, 2046.9 parts of deionized water was added with stirring to obtain an aqueous dispersion.

Next, with respect to 300 parts of the above-mentioned aqueous dispersion, 62 parts of each red dispersion was prepared by adding each color dispersion prepared in Reference Example 4, respectively.
Electrodeposition composition for red mixed with 7 parts of yellow dispersion liquid and 46 parts of deionized water, 31.5 parts of green dispersion liquid, 13.5 parts of yellow dispersion liquid and 105 parts of deionized water Electrodepositing composition for blue, which was obtained by mixing the following substances: blue dispersion 29 parts, purple dispersion 7 parts, deionized water 162 parts, black dispersion 45 parts and deionized water 105.
An electrodeposition composition for black was prepared by mixing the parts.

Next, the positive type photosensitive resin composition prepared in Reference Example 3 was formed on a glass substrate (made by Asahi Glass) on the surface of which an ITO film (indium-tin oxide) was formed by a known method by a spinner. It was applied to a thickness of 2.5μ.
On this film, an exposure device (MAP-1200L,
An exposure amount of 500 mj / cm ² was applied by Dainippon Screen. Then, the film was developed with a 5% aqueous solution of dimethylethanolamine at 40 ° C. for 2 minutes and dried at 135 ° C. for 10 minutes to expose the ITO surface corresponding to the red colored layer.

This substrate was immersed in the above-mentioned bath for electrodeposition coating composition for red adjusted to 23 ° C., and the exposed ITO surface without pixels around the substrate was used as an electrode contact, and electricity was applied at 35 V for 5 seconds. This substrate was immediately washed with water and dried at 155 ° C. for 10 minutes to form a smooth red colored layer having a film thickness of 2 μm and free from pinholes due to partial repelling. An exposure amount of 500 mj / cm ² was applied to this substrate similarly to red through a mask having a green pixel portion which transmits light and the other portion having a light shielding property. Then, similarly, using a 5% aqueous solution of dimethylethanolamine, 4
It was developed at 0 ° C. for 2 minutes and dried at 135 ° C. for 10 minutes to expose the ITO surface corresponding to the green colored layer. During this development process, no defects such as floating, peeling, and film thickness reduction were observed on the red colored layer. In the same manner, a green colored layer was formed under the conditions of electrodeposition at 30 V for 5 seconds, and then a blue colored layer was formed by exposing and developing the blue pixel portion under the same conditions and electrodeposition at 40 V for 5 seconds. During this period, no defective phenomenon such as floating, peeling, and film thickness reduction was observed on any of the colored films.

Further, the above substrate was 500 mj / c without a mask.
The entire surface of m ² was exposed, and the development treatment was performed in the same manner to remove the remaining photosensitive resin composition. At this time, no defective phenomenon was observed in each colored layer. Then, it was immersed in the above-mentioned black electrodeposition coating composition bath, electrified at 40 V for 5 seconds to form a black light-shielding layer, and dried at 155 ° C. for 10 minutes. Then, it was baked at 250 ° C. for 2 hours to prepare a color filter colored layer.

This substrate was further subjected to heat treatment at 250 ° C. for 1 hour, and the values of coordinates (x, y) in the CIE chromaticity diagram before and after the heat treatment were measured by the color analyzer TC-1800M.
When measured with a (C light source, 2 ° field of view, manufactured by Tokyo Denshoku Co., Ltd.), the amounts of change in red, green, and blue were all within 0.01, and the heat resistance was excellent. In addition, this substrate was subjected to a light resistance accelerated test (200 hours of light irradiation by Suntester XF-180,
The same change amount of coordinates (x, y) by Shimadzu Corporation was within 0.01 for each of red, green, and blue, which was also excellent in light resistance.

Example 2 The same procedure as in Example 1 was carried out except that the above-mentioned (ii) was used as the compound having a hydroxyl group and a siloxane skeleton. No change was observed, and in the heat and light resistance tests, the amount of change in coordinates (x, y) was good within 0.01.

Example 3 Anionic acrylic resin composition 800 shown in Reference Example 1
Parts, 50 parts of the compound (i) having the siloxane resin skeleton described above, and hexamethoxymethylated melamine 5
After mixing 0 parts and 15.5 parts of triethylamine, 1877.8 parts of deionized water was added with stirring to obtain an aqueous dispersion.

Next, with respect to 300 parts of the above aqueous dispersion, 62 parts of each red dispersion prepared by adding each color dispersion prepared in Reference Example 4,
Electrodeposition composition for red mixed with 7 parts of yellow dispersion liquid and 46 parts of deionized water, 31.5 parts of green dispersion liquid, 13.5 parts of yellow dispersion liquid and 105 parts of deionized water Electrodepositing composition for blue, which was obtained by mixing the following substances: blue dispersion 29 parts, purple dispersion 7 parts, deionized water 162 parts, black dispersion 45 parts and deionized water 105.
An electrodeposition composition for black was prepared by mixing the parts.

Thereafter, when the same procedure as in Example 1 was performed, no defects such as floating, peeling, and film thickness reduction on the colored film were observed throughout the entire process, and the coordinates (x,
The change amount of y) was good within 0.01.

Comparative Example 1 Anionic acrylic resin 692.3 shown in Reference Example 1
Parts, 50 parts of hexamethoxymethylated melamine and 17.4 parts of triethylamine were mixed, and then, with stirring, 2018.1 parts of deionized water was added to obtain an aqueous dispersion. Next, an electrodeposition composition for red obtained by mixing 62 parts of the red dispersion liquid, 7 parts of the yellow dispersion liquid and 46 parts of deionized water with 300 parts of the above-mentioned water dispersion liquid of each color dispersion liquid prepared in Reference Example 3, Electrodeposition composition for green mixed with 31.5 parts of green dispersion, 13.5 parts of yellow dispersion and 105 parts of deionized water, blue dispersion 29
Parts, purple dispersion liquid 7 parts, deionized water 162 parts were mixed to prepare a blue electrodeposition composition, and black dispersion liquid 45 parts and deionized water 105 parts were mixed to prepare a black electrodeposition composition.

Next, as in Example 1, a glass substrate having an ITO film (indium-tin oxide) formed on its surface) Reference Example 3
The positive photosensitive resin composition of No. 2 was used to form a film with a spinner to a film thickness of 2.5.
It was applied so that the thickness would be μ. On this film, an exposure amount of 500 mj / cm ² was applied by an exposure device (MAP-1200L, manufactured by Dainippon Screen) through a mask having a red pixel portion transmitting light and the other portion having a light shielding property. Then, the film was developed with a 5% aqueous solution of dimethylethanolamine at 40 ° C. for 2 minutes and dried at 135 ° C. for 10 minutes to expose the ITO surface corresponding to the red colored layer.

This substrate was immersed in the above-mentioned bath composition for red electrodeposition coating composition adjusted to 23 ° C., and the exposed ITO surface without pixels around the substrate was used as an electrode contact and electricity was applied at 35 V for 5 seconds. This substrate was quickly washed with water and dried at 155 ° C. for 10 minutes to form a smooth red colored layer having a film thickness of 2 μm. An exposure amount of 500 mj / cm ² was applied to this substrate similarly to red through a mask having a green pixel portion which transmits light and the other portion having a light shielding property. Then, the film was similarly developed using a 5% aqueous solution of dimethylethanolamine at 40 ° C. for 2 minutes, and the previously electrodeposited red colored layer was partially peeled off, and formation of the colored layer thereafter was stopped. .

Comparative Example 2 Anionic acrylic resin 615.4 shown in Reference Example 1
Parts, linear polydimethylsiloxane (trade name KF-96-
100CS, manufactured by Shin-Etsu Chemical Co., Ltd.) 50 parts, hexamethoxymethylated melamine 50 parts and triethylamine 15.5.
The parts were mixed. At this time, a phenomenon in which the mixed varnish became cloudy was observed.
An aqueous dispersion was obtained by adding 6.9 parts.

Next, with respect to 300 parts of the above-mentioned aqueous dispersion, 62 parts of each of the color dispersions prepared in Reference Example 3 and red dispersion,
Electrodeposition composition for red mixed with 7 parts of yellow dispersion liquid and 46 parts of deionized water, 31.5 parts of green dispersion liquid, 13.5 parts of yellow dispersion liquid and 105 parts of deionized water Electrodepositing composition for blue, which was obtained by mixing the following substances: blue dispersion 29 parts, purple dispersion 7 parts, deionized water 162 parts, black dispersion 45 parts and deionized water 105.
An electrodeposition composition for black was prepared by mixing the parts.

Next, as in Example 1, a glass substrate having an ITO film (indium-tin oxide) formed on its surface) Reference Example 3
The positive photosensitive resin composition of No. 2 was used to form a film with a spinner to a film thickness of 2.5.
It was applied so that the thickness would be μ. On this film, an exposure amount of 500 mj / cm ² was applied by an exposure device (MAP-1200L, manufactured by Dainippon Screen) through a mask having a red pixel portion transmitting light and the other portion having a light shielding property. Then, the film was developed with a 5% aqueous solution of dimethylethanolamine at 40 ° C. for 2 minutes and dried at 135 ° C. for 10 minutes to expose the ITO surface corresponding to the red colored layer.

This substrate was immersed in the above-mentioned bath for electrodeposition coating composition for red adjusted to 23 ° C., and the exposed ITO surface without pixels around the substrate was used as an electrode contact, and electricity was applied at 35 V for 5 seconds. When this substrate was immediately washed with water and dried at 155 ° C. for 10 minutes, the mixed silicone compound migrated to the surface of the colored film to form a liquid film and a uniform film was not formed, and the subsequent steps were stopped.

[0076]

The compound having a hydroxyl group and a siloxane skeleton used in the present invention is compatible with a polymer resin having an ionic group and is uniformly dispersed in the electrodeposition coating film, and the compound having a short period of time is used for the electrodeposition coating film. The heat treatment also provides sufficient color resistance to the developer used for removing the exposed portion of the photosensitive resin composition and provides a color filter colored layer excellent in heat resistance and light resistance.

[Brief description of drawings]

FIG. 1 is a process chart of the manufacturing method of the present invention, (A)
(M) is a sectional view.

FIG. 2 is a process drawing of the second manufacturing method of the present invention,
(A)-(Q) is sectional drawing.

[Explanation of symbols]

1: substrate, 2: transparent conductive film, 3: photosensitive resin layer, 4: mask, 5: 1 color layer, 6: second color layer, 7: third color layer, 8: black matrix layer.

Continuation of front page (51) Int.Cl. ⁶ Identification number Internal reference number FI Technical display location G02F 1/1335 G02F 1/1335 (72) Inventor Koji Osugi 19-17 Ikedanaka-cho, Neyagawa-shi, Osaka Japan Paint Within the corporation

Claims (6)

[Claims] 1. A polymer resin having an ionic group and having water solubility or water dispersibility, and a compound having a hydroxyl group and a siloxane skeleton in the molecule in a solid content ratio of 30:70 to 99 :.
An electrodeposition coating composition for forming a color filter, comprising a resin mixture contained in a ratio of 1 and a colorant. 2. An electrodeposition coating composition for forming a color filter according to claim 1, wherein the compound having a hydroxyl group and a siloxane skeleton in the molecule is a compound represented by the following general formula (I): (In the formula, R ¹ is methyl, 3-hydroxypropyl or 3-
(Hydroxyethoxy) propyl group, R ² and R ³
Are independently methyl, phenyl, phenylethyl, 3-hydroxypropyl, or 3- (hydroxyethoxy) propyl groups, R ⁴ is a methyl, phenyl, or phenylethyl group, and R ⁵ is methyl, phenyl, phenyl. Is an ethyl or isobutyl group, and at least one of R ¹ and R ³ is a terminal hydroxyl group, l is an integer of 2 to 4, and m is an integer of 1 to 30. ,
n is an integer of 0-2). 3. A step of (a) forming a photosensitive resin film on a transparent conductive layer surface of a substrate having a transparent conductive layer on the surface,
(B) The photosensitive resin film is exposed through a mask having a pattern corresponding to a desired colored layer site, and then developed to form a resist opening corresponding to the desired pattern to form a part of the transparent conductive layer. Exposing step, (c)
Steps (a) to (d), which include a step of forming a colored layer of a desired color by electrodeposition of an electrodeposition coating composition on the site, and (d) a step of peeling off an unnecessary photosensitive resin film. A method for producing a color filter colored layer for a multicolor display device by repeating the above step, wherein the electrodeposition coating composition comprises a polymer resin having an ionic group and having water solubility or water dispersibility, and a molecule. A method for producing a color filter colored layer, comprising a resin mixture containing a compound having a hydroxyl group and a siloxane skeleton in a solid content ratio of 30:70 to 99: 1, and a colorant. 4. The method for producing a color filter colored layer according to claim 3, wherein the compound having a hydroxyl group and a siloxane skeleton in the molecule is a compound represented by the following general formula (I): (In the formula, R ¹ is methyl, 3-hydroxypropyl or 3-
(Hydroxyethoxy) propyl group, R ² and R ³
Are independently methyl, phenyl, phenylethyl, 3-hydroxypropyl, or 3- (hydroxyethoxy) propyl groups, R ⁴ is a methyl, phenyl, or phenylethyl group, and R ⁵ is methyl, phenyl, phenyl. Is an ethyl or isobutyl group, and at least one of R ¹ and R ³ is a terminal hydroxyl group, l is an integer of 2 to 4, and m is an integer of 1 to 30. ,
n is an integer of 0-2). 5. (a) A step of forming a photosensitive resin film on the transparent conductive layer surface on a substrate having a transparent conductive layer on the surface,
(B) The photosensitive resin film is exposed through a mask having a pattern corresponding to a desired colored layer site, and then developed to form a resist opening corresponding to the desired pattern to form a part of the transparent conductive layer. And (c) a step of forming a colored layer of a desired color by electrodeposition of an electrodeposition coating composition on the site, and (b)-
A method for producing a color filter colored layer for a multicolor display device by repeating the step (c) a required number of times, wherein the electrodeposition coating composition has an ionic group and is water-soluble or water-dispersible. The resin and the compound having a hydroxyl group and a siloxane skeleton in the molecule are in a solid content ratio of 30:70 to 99 :.
1. A method for producing a colored layer of a color filter, which comprises a resin mixture contained in a ratio of 1 and a colorant. 6. The method for producing a color filter colored layer according to claim 5, wherein the compound having a hydroxyl group and a siloxane skeleton in the molecule is a compound represented by the following general formula (I): (In the formula, R ¹ is methyl, 3-hydroxypropyl or 3-
(Hydroxyethoxy) propyl group, R ² and R ³
Are independently methyl, phenyl, phenylethyl, 3-hydroxypropyl, or 3- (hydroxyethoxy) propyl groups, R ⁴ is a methyl, phenyl, or phenylethyl group, and R ⁵ is methyl, phenyl, phenyl. Is an ethyl or isobutyl group, and at least one of R ¹ and R ³ is a terminal hydroxyl group, l is an integer of 2 to 4, and m is an integer of 1 to 30. ,
n is an integer of 0-2).