JP2828864B2 - Multicolor pattern formation method using polysilane - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for forming a colored pattern on a substrate, and more particularly to a method for manufacturing a color filter for a color liquid crystal display.

[0002]

2. Description of the Related Art A color filter is used for color display of a liquid crystal display using a liquid crystal as an optical shutter.

[0003] The main methods for producing color filters include a dyeing method, a color resist method, an electrodeposition method and a printing method.

[0004] Among the methods for manufacturing such color filters, in the dyeing method, the color resist method, and the electrodeposition method, in order to form three primary colors of red, green, and blue (RGB) on a filter material, it is necessary to use each color. A photolithography process including a wet development process is required. Therefore, the manufacturing process is complicated, the yield is low, and it is difficult to reduce the cost.

[0005] The printing method does not require a photolithography step, so the manufacturing process is relatively simple. However, the position of the formed RGB pattern cannot be strictly controlled. Therefore, the pattern is disturbed due to blistering or thinning of the end of the black matrix.

[0006] Under such circumstances, there is a demand for a colored pattern forming method which can be manufactured at low cost because the process is simple and can obtain a color filter having excellent pattern definition.

The present inventors previously proposed a method of sequentially dyeing a single polysilane layer without mixing a multicolor pattern by selecting a dye (Japanese Patent Application No. 4-4539), A method of immersing in a colored sol solution using pigment and metal alkoxide as raw materials and successively coloring a multicolor pattern without mixing colors
(Japanese Patent Application No. 4-68243). These methods are simple methods in which a polysilane layer having a latent image formed by ultraviolet irradiation can be dyed or colored simply by immersing it in a dyeing or coloring bath. However, diffusion development of a dye or pigment into the polysilane layer is carried out. Therefore, there is a problem that it takes time to obtain a desired dark color pattern.

On the other hand, a method called an electrodeposition method has been proposed in which a charged polymer or charged particles in a bath is deposited on an electrode to obtain a colored pattern. JP-A-59-114572 discloses a charged polymer in which a carboxyl group in a molecule is neutralized and solubilized with an inorganic alkali, an organic amine or the like, or a basic group (eg, polyamine) in a molecule is neutralized with an acid. A method is disclosed in which a water-soluble material is used to precipitate on an electrode, and then the precipitated polymer is dyed with a reactive dye.

Japanese Patent Application Laid-Open No. 60-184696 discloses an example in which a polymer having a dye chemically bonded thereto is deposited on an electrode.

JP-A-63-243298 discloses that a hydrophobic organic substance such as a pigment is solubilized in an aqueous medium with a micellizing agent comprising a ferrocene derivative, and the resulting micellar solution is electrolyzed to form an electrode. A method for forming a thin film of the hydrophobic organic material is disclosed.

The method of forming a colored pattern by utilizing the reaction between the electrophoresis and the electrode is characterized in that the obtained colored pattern has excellent dimensional accuracy. However, in these methods, the same electrode pattern as the pattern to be obtained must be prepared in advance. ITO
A method of etching electrodes and the like using a pattern resist formed by a photolithography method is mainly employed. However, this photolithography method has a problem that the steps are complicated and the productivity is poor. Also, as a color filter pattern, it is known that a mosaic pattern can provide a visually superior effect.However, since these methods can only obtain the same hue color on the same electrode, the mosaic pattern is Cannot be formed.

[0012]

SUMMARY OF THE INVENTION An object of the present invention is to solve the problems of the polysilane method and the electrodeposition method described above and to provide a simple and highly productive color filter manufacturing method.

[0013]

According to the present invention, there is provided a method comprising the steps of: a) providing a transparent electrode layer on a substrate;

[0014]

Embedded image

(Wherein R ₁ , R ₂ , R ₃ and R ₄ are each independently selected from the group consisting of substituted or unsubstituted aliphatic hydrocarbon residues, alicyclic hydrocarbon residues and aromatic hydrocarbon residues. And m and n are integers.) A step of forming a latent image of a colored pattern by selectively irradiating a polysilane layer comprising a polysilane having a structure represented by the formula: D) immersing the polysilane layer on which the latent image of the colored pattern is formed in an electrodepositable solution containing at least one dye or pigment, and electrodeposition-patterning the latent image portion with a pattern; Except for forming a latent image of a different coloring pattern on the polysilane layer and using a different dye or pigment, at least one
The present invention provides a method for forming a multicolored pattern on a polysilane layer, which includes a separate pattern coloring step performed repeatedly, whereby the above object is achieved.

The polysilane used in the present invention has the formula

[0017]

Embedded image

(Wherein R ₁ , R ₂ , R ₃ and R ₄ are methyl, n-propyl, n-butyl, n-hexyl, phenylmethyl, trifluoropropyl and nonafluorohexyl) Substituted or unsubstituted aliphatic hydrocarbon residues such as p-tolyl group, biphenyl group and phenyl group, and substituted or unsubstituted alicyclic rings such as cyclohexyl group and methylcyclohexyl group Are groups independently selected from the group consisting of hydrocarbon residues, and m and n are integers.) When aliphatic or alicyclic hydrocarbon has a carbon number of 1 to 10, in the case of aromatic hydrocarbons, the kind of R ₁ to R ₄ groups are 6 to 14 carbon atoms, and m and n values Is not particularly important, because this polysilane resin is soluble in organic solvents,
(A thickness of 0.5 to 10 [mu] m) as long as it can be coated.

However, in general, as the molecular weight of polysilane decreases, the organic solvent resistance of the formed polysilane layer decreases. Therefore, when a polysilane layer is formed using low molecular weight polysilane, when the amount of the organic solvent contained in the electrodeposition solution is large, the polysilane layer partially dissolves in the electrodeposition solution, and a pinhole is formed in the polysilane layer during electrodeposition. Or uneven coloring. Accordingly, polysilanes having a weight average molecular weight above 10,000 are particularly preferred for the polysilane layers of the present invention.

Such polysilanes can be prepared, for example, by converting a plurality or a single diorganodichlorosilane into toluene or n-decane solvent in the presence of sodium metal.
It is adjusted by heating and reacting at a temperature exceeding 0 ° C. for 3 hours or more.

Specific examples of preferred polysilanes that can be used in the present invention include polyphenylmethylsilane in which R ₁ is a methyl group and R ₂ is a phenyl group, R ₁ is a methyl group,
R ₂ is a phenyl group, R ₃ is a methyl group, R ₄ is polyphenyl methyl / methyl trifluoropropyl silane and the like trifluoropropyl group.

The adverse effects at the time of coloring due to partial redissolution of the polysilane layer can be prevented by blending a crosslinking agent into the polysilane layer to improve the organic solvent resistance of the polysilane layer. As a crosslinking agent that can be used in the polysilane layer of the present invention,
For 100 parts by weight of silicone oil having silanol groups at both ends such as polydimethylsiloxane diol, 2 to 10 parts of trifunctional silane such as acetoxysilane, oxime silane and aminooxysilane, and tin compound and platinum compound Metal catalyst such as 0.0
It is preferable to use a silicone rubber composition consisting of 5 to 1 part. Such a silicone rubber composition crosslinks the polysilane layer by a condensation reaction due to moisture and improves the organic solvent resistance of the polysilane layer. The compounding amount of the silicone rubber composition is 0.01 per 100 parts by weight of polysilane.
It is preferably from 50 to 50 parts by weight, particularly preferably from 1 to 10 parts by weight. When the amount is less than 0.01 part by weight, sufficient solvent resistance is not imparted to the polysilane layer, and when the amount exceeds 50 parts by weight, the colorability at the time of electrodeposition decreases.

As the electrodepositable solution containing at least one dye or pigment used in the present invention, a solution known per se can be used.

That is, a resin having an acid group is neutralized with an inorganic alkali, an organic amine or the like, and an anion electrodeposition type aqueous solution or aqueous dispersion obtained by dissolving or dispersing in a solvent mainly composed of water together with a pigment is used. A water-insoluble pigment can be added to a cationic electrodeposition-type aqueous solution in which the resin is neutralized with an acid and dissolved or dispersed together with the pigment in a solvent mainly composed of water, or an aqueous micelle aqueous solution of a charged surfactant. Examples thereof include a solubilized aqueous solution and a dispersed aqueous dispersion.

Examples of the resins belonging to the above-mentioned types include an adduct of a natural drying oil and maleic acid, an alkyd resin having a carboxyl group introduced therein, an epoxy resin having a maleic acid added thereto, a polybutadiene resin having a carboxyl group introduced therein, acrylic acid or methacrylic acid. Copolymers of an acid (hereinafter abbreviated as (meth) acrylic acid) and a vinyl monomer are exemplified. Among them, (meth) acrylic acid copolymers and oil-free polyester resins are preferable as those having excellent transparency.

The resins belonging to the above-mentioned types include amine-added epoxy resins obtained by reacting an amine compound with an epoxy resin, amine-added epoxidized polybutadiene resins obtained by reacting an amine compound with epoxidized polybutadiene, and tertiary resins. A copolymer of a (meth) acrylic acid ester having an amino group and a vinyl monomer is exemplified. Among them, what is excellent in transparency,
(Meth) acrylate copolymers are preferred.

The surfactant belonging to the above type may be any one which is positively or negatively charged. Examples of the positively charged surfactant include benzalkonium chloride, lanolin fatty acid aminopropylethyl dimethyl ammonium salt, Tetraalkyl ammonium salt,
And imidazolinium salts and alkyldimethylbenzylammonium salts. Examples of negatively charged ones include aliphatic carboxylate, alkylbenzene sulfonate, sulfosuccinate and the like.

Among these surfactants, JP-A-1-31
6492, poly (oxyethylene) 11-
Ferrocenyl undecyl ether, ferrocenyl methyl dodecyl dimethyl ammonium bromide, ferrocenyl undecyl pyridinium bromide and the like are preferred.

As the dye that can be used in the present invention, those known per se can be used, and direct dyes, acid dyes, basic dyes,
Oil-soluble dyes and disperse dyes. Examples of CI No. of dyes that can be suitably used in the present invention are shown below.

As the direct dye, direct yellow
(Direct Yellow) 44, Direct Red (Direct Re)
d) 23, Direct Red 79, Direct Blue
(Direct Blue) 25, Direct Blue 86, Direct Green 59 and the like.

As the acid dye, acid yellow (A
cid Yellow) 38, Acid Yellow 99, Acid Violet 49, Acid Blue
(AcidBlue) 40, Acid Blue 83, Acid Green 25, Acid Green 18 and the like.

As basic dyes, basic red
(Basic Red) 12, Basic Violet (Basic Vi
olet) 7, Basic Violet 10, Basic Violet 40, Basic Blue
1, Basic Blue 7, Basic Blue 26,
Basic Blue 77, Basic Green (Basic
Green) 1 and Basic Yellow
21 and the like.

The oil-soluble dyes include Solvent Red
(Solvent Red) 125, Solvent Red 132, Solvent Red 83, Solvent Red 109, Solvent Blue (Solvent Blue) 67, Solvent Blue 25, Solvent Yellow (Solvent Yellow) 2
5, Solvent Yellow 89, Solvent Yellow 146, and the like.

As the disperse dye, Disperse Red
(Disperse Red) 60, Disperse Red 72, Disperse Blue 56, Disperse Blue 60, Disperse Yell
ow) 60 and the like.

Of these, direct dyes, acid dyes and metal-containing oil-soluble dyes which are particularly excellent in heat resistance and light resistance are suitable as color filter materials.

As the pigment used in the present invention, known inorganic pigments and organic pigments can be used. As inorganic pigments, Pigment Yellow (Pigment Yellow) 34, Pigment Yellow
Yellow 37, Pigment Red 10
1, Pigment Red 105, Pigment Red 1
08, Pigment Violet 1
6, Pigment Blue 27, Pigment Blue 29, Pigment Green
n) 17, Pigment Green 18, Pigment Black 7, and the like. Is mentioned.

As organic pigments, Pigment Red (P
igment Red) 177, Pigment Red 220, Pigment Red 221, Pigment Red 53: 1,
Pigment Blue 15: 3, Pigment Blue 15, Pigment Blue 60, Pigment Green 7, Pigment Green 36, Pigment Violet 2
3, Pigment Violet 37, Pigment Yellow 83, and the like.

As a method of preparing an electrodepositable solution, in the case of an anionic electrodeposition solution containing a resin, a resin having an acid group is neutralized with a base to form an aqueous solution or aqueous dispersion, and a dye or a water dispersion is added thereto. It is prepared by dissolving or dispersing a pigment. As a dispersion means, a three-roll mill, an SG mill, an ultrasonic homogenizer, a mechanical homogenizer, or the like is used. When a pigment is used, it is necessary to make it into fine particles in order to obtain a colored pattern having good transparency, and it is preferable to disperse the particles so that the particle diameter becomes 0.4 μm or less, and to classify the particles if necessary. Thereafter, the mixture is diluted with water so that the pigment concentration becomes 3 to 20%, and if necessary, a solvent is added to obtain an electrodeposition solution. Further, a thermosetting electrodeposition solution can be prepared by adding an amino resin such as hexamethoxymethylmelamine as a crosslinking agent. In addition, a silane coupling agent having a carboxyl group (e.g., Shin-Etsu Chemical Co., Ltd., X-12-650B) in order to react with a silanol group generated in an ultraviolet irradiation portion of polysilane to form a crosslinked structure.
Alternatively, alkaline colloidal silica (for example, Nissan Chemical Industries, Snowtex-N) can be used. In the case of a water-soluble dye, a dispersing step is not required. However, in the case of an oil-soluble dye or a disperse dye, it is necessary to disperse and atomize the dye in the same manner as a pigment.

As a method for preparing a cationic electrodeposition solution containing a resin, a resin having a basic group is neutralized with an acid to form an aqueous solution or an aqueous dispersion, and a dye or a dye is prepared in the same manner as in the case of the above-mentioned anionic electrodeposition solution. It is prepared by dissolving or dispersing a pigment. In order for the electrodeposited film to form a crosslinked structure, a crosslinking agent may be used in combination. For example, those using both terminal amine-modified epoxy resin and blocked isocyanate are electrodeposited to form a coating, and then dried by heating.
Generate isocyanate from blocked isocyanate,
This reacts with the amino group or hydroxyl group of the amine-modified epoxy resin to form a crosslinked structure. As the blocked isocyanate, a block of hexamethylene diisocyanate, xylene diisocyanate, isophorone diisocyanate, or the like, and phenol or methyl ethyl ketone oxime can be used. In order to form a crosslinked structure with the silanol group of the polysilane layer, a silane coupling agent having a basic group such as aminopropyltriethoxysilane or acidic colloidal silica can be used in combination.

As a method for preparing an electrodeposition solution comprising a surfactant and a dye or a pigment, the electrodeposition solution is prepared by adding the surfactant and the dye or the pigment in an aqueous medium. In the case of a pigment, the pigment is made into fine particles using a mechanical homogenizer, an ultrasonic homogenizer, a three-roll mill, an SG mill, or the like. By this operation, the pigment is uniformly dispersed or solubilized in an aqueous medium to form a dispersion or an aqueous solution. The concentration of the surfactant is not particularly limited, but is preferably not less than the critical micelle concentration. In order to form a crosslinked structure with the silanol group of the polysilane layer, the above-mentioned silane coupling agent or colloidal silica can be used in combination. A supporting electrolyte may be added as needed to adjust the electrical conductivity. Sulfates (salts such as lithium, potassium, and sodium) and acetates (salts such as lithium, potassium, and sodium) are preferred.

In the pattern forming method of the present invention, first, a transparent electrode is formed on a glass plate. As a transparent electrode material, I
TO (mixed oxide of indium oxide and tin oxide), and a conductive polymer. It is formed on a glass plate by these sputtering method, spray method or spin coating method.

Further, a polysilane layer is formed thereon,
Create a color filter material. A solution containing the above-mentioned polysilane and, if necessary, a crosslinking agent may be applied on the ITO layer and dried. The formation method is not particularly limited as long as a polysilane layer having a uniform thickness can be formed. Generally, it is preferable to use a spin coating method. The organic solvent used in the polysilane layer forming step is not particularly limited as long as it is an evaporable organic solvent capable of dissolving polysilane. Toluene and n-decane are preferably used. If the thickness of the polysilane layer is too large, the resistance of the UV irradiating part becomes large and electrodeposition cannot be performed. On the other hand, if it is too thin, the non-irradiated portion does not serve as a barrier at the time of electrodeposition, and cannot be formed in an accurate pattern. When used as a color filter, it is preferable to form a dry thickness of 0.5 to 10 μm.

One example of the step of coloring the obtained filter material in a multicolor pattern is shown in FIGS. 1 (a) to 1 (f). First, as shown in FIG. 1A, the base 1 obtained as described above is used.
The filter material 104 composed of 01, the ITO layer 102 and the polysilane layer 103 is irradiated according to a pattern using ultraviolet rays such as a mercury lamp. The irradiation of the ultraviolet rays 105 is performed through a mask film 106 having a pattern superimposed on the filter material 104.

The ultraviolet rays used in the present invention may be those having a wavelength of 250 to 400 nm, which is the ultraviolet absorption range of polysilane. Examples thereof include a medium-pressure mercury lamp, an ultra-high-pressure mercury lamp, a xenon lamp, and a metal halide lamp. This irradiation is preferably performed at a light amount of 0.5 to ¹⁰ J / cm ² . When the irradiation light quantity is less than 0.5 J / cm ² , the coloration at the time of electrodeposition decreases, and when it exceeds 10 J / cm ² , the occurrence of pinholes increases.

Next, the filter material on which the latent image is formed is immersed in an electrodeposition solution, and the ITO layer is electrodeposited as a cathode or an anode, thereby forming a colored pattern on the polysilane layer of the latent image. If necessary, a water-soluble organic solvent such as acetonitrile, dioxane, and tetrahydrofuran may be added to swell the polysilane layer in the latent image forming portion to increase the coloring speed and the coloring concentration. Such a water-soluble organic solvent is preferably contained in the electrodeposition solution in an amount of 1 to 20% by weight. When the content of the solvent is more than 20% by weight, the polysilane layer is partially dissolved, which may cause uneven coloring.

The colored filter material is dried after removing the electrodeposition solution. As a method of removing the electrodeposition liquid,
A method of washing with water, a method of blowing off with air blow, and the like can be used.

When the resin used in the electrodeposition solution has a crosslinking ability, the resin may be dried at a predetermined temperature and for a predetermined time in accordance with the conditions of the crosslinking reaction. If the resin used in the electrodeposition solution does not have a crosslinking ability, or if the resin does not contain a pigment and a surfactant, the temperature and time conditions under which the solvent can be removed from the system may be sufficient, It is preferable to dry at 80 ° C. for 10 minutes or more in order to prevent color mixing in the case of successively performing multicolor coloring. In the case of micellar electrolysis, as a method for preventing color mixing, the oxidation potential of the pigment used is measured by voltammetry, and if the polysilane layer is colored by electrolysis from a pigment having a high oxidation potential, a drying step or a crosslinking agent Can be prevented from mixing in the next electrolysis step. For example, chlorinated copper phthalocyanine (CI Pigm
ent Green 7) and copper phthalocyanine (CI Pigment Blue 15)
Are 1.2V and 0.9V, respectively, and the polysilane layer is colored green at 1.2V using a micellar solution of chlorinated copper phthalocyanine. Subsequently, when electrolysis is performed at 0.9 V using a micellar solution of copper phthalocyanine, the chlorinated copper phthalocyanine previously deposited is not oxidized and has no conductivity. can do.

If a filter material having a multicolor pattern, such as a color filter, is desired, then, as shown in FIG. 1C, the polysilane layer is formed by using a mask film 116 instead of the mask film 106. Except for forming latent images of different colored patterns and using dyes or pigments exhibiting other hues, in the same manner as in the first pattern coloring step, as shown in FIG.
A filter material 104 "colored in a pattern is obtained (second pattern coloring step). The mask film 116 used here generally has the first pattern coloring of the polysilane layer as shown in FIG. 1 (c). It has a mask pattern that covers the colored pattern portion in the process and exposes the uncolored portion.

Further, if desired, as shown in FIG. 1E, a latent image having a different color pattern is formed on the polysilane layer by using a mask film 126 instead of the mask film 116, and further, other color images are formed. Except for using the dye and pigment of the above, in the same manner as in the second pattern coloring step,
As shown in Fig. 1 (f), a filter dye 104 '"colored in a desired three colors is obtained (third pattern coloring step). The mask film 126 used here is
In general, as shown in FIG. 1 (e), a mask pattern that covers the pattern portion of the polysilane layer that has been colored in the first pattern coloring step and the second pattern coloring step and exposes the uncolored portion is formed. Have

By repeating such a process, it is possible to produce a filter material which is further colored in a multi-color pattern. Further, in the example shown here, the colored patterns formed on the polysilane layer in the first, second, and third pattern coloring steps are formed so as not to overlap with each other. However, the term "forming latent images of different patterns" in this specification refers to not forming latent images of exactly the same coloring pattern in each pattern coloring step, and is not necessarily colored so as not to overlap with each other. It is not limited to forming a pattern. Also, "using different dyes or pigments" herein
The term refers to the use of an electrodeposition solution having a different hue containing at least one dye or pigment in each pattern coloring step, and a part of the dye or pigment composition used in the electrodeposition solution is used in each step. May overlap.

As described above, the pattern coloring method of the present invention does not require a photolithography step including a wet development step for forming a colored pattern. Also, the pattern-colored filter material obtained by this method has an essentially flat surface since it consists of a single polysilane layer formed on a transparent substrate. Therefore, a polishing step for smoothing the surface and a step of coating the flattening layer on the surface are unnecessary. Furthermore, there is no need to use a dye-resistant layer for preventing color mixing. As a result, the steps of the colored pattern forming method are significantly simplified.

The obtained pattern-colored filter material has a flat surface and does not cause color mixing between the colored patterns, so that it has excellent pattern definition.

Further, since a pigment excellent in heat resistance and light resistance can be used as a coloring material, deterioration of the coloring material in a heating step in the production of a color display can be prevented.

The present invention is particularly suitable for producing a color filter for a color liquid crystal display. In that case, dyes or pigments corresponding to the three primary colors RGB are used in the first, second, and third pattern steps described above, respectively. Further, it is also possible to form a black stripe by using a black dye or pigment in the fourth pattern coloring step. Needless to say, the fourth pattern coloring step does not necessarily need to be performed after the RGB three primary color pattern coloring, and the RGB three primary color pattern coloring may be performed in advance on the filter material on which the black stripe is formed.

[0055]

According to the present invention, a latent image having a colored pattern is formed by exposing the polysilane layer to ultraviolet light. Although the principle has not been elucidated, a portion where the ultraviolet light is irradiated on the polysilane layer becomes conductive, and electrodeposition becomes possible. At present, it is thought that the UV-irradiated part may become porous, but it is not certain. In any case, the exposed portion can be electrodeposited, and a pigment or dye is deposited on the polysilane layer to form a colored pattern. This method is a simple and highly productive method for producing a color filter.

[0056]

The present invention will be further described with reference to the following examples, but the present invention is not limited to these examples. “%” And “parts” used in this example are all based on weight.

Preparation Example 1 "Example of synthesis of polyphenylmethylsilane" 400 ml of toluene was placed in a 1000 ml flask equipped with a stirrer.
And 13.3 g of sodium. After finely dispersing sodium in toluene by high-speed stirring,
Here, 51.6 g of phenylmethyldichlorosilane was added. Next, the contents of this flask were heated to 111 ° C. in a yellow room where ultraviolet rays were shielded, and stirred for 5 hours to carry out polymerization. Then, excess sodium was deactivated by adding ethanol to the obtained reaction mixture, and the organic layer was separated by washing with water. The polysilane was precipitated by pouring the organic layer into ethanol. By recrystallizing the obtained crude polyphenylmethylsilane three times in ethanol, polyphenylmethylsilane having a weight average molecular weight of 200,000 was obtained.

Preparation Example 2 "Preparation Example of Cation Electrodeposition Liquid" An electrodeposition liquid for red coloring was prepared by the following method. 17780 parts by weight of CI Pigment Red and 20 parts by weight of CI Pigment Yellow 83 were mixed with 30 parts by weight of an imidazoline surfactant (imidazoline C manufactured by Nippon Emulsifier Co.) and 300 parts by weight of ion-exchanged water, and then mixed with a sand mill.
Ion-exchanged water was added again to the dispersion that had been dispersed for time and filtered under pressure to adjust the pigment concentration to 10%, and acetonitrile was added to the electrodeposition solution to 15%. The electrodeposition liquid for green coloring is composed of 90 parts by weight of CI Pigment Green 36 and CI Pigment Yellow 83 10
It was prepared in the same manner as in the electrodeposition solution for red coloring using parts by weight. The electrodeposition solution for blue coloring is CI Pigment Blue 1
5 80 parts by weight, CI Pigment Violet 232
It was prepared in the same manner as the red coloring electrodeposition solution using 0 parts by weight.

Preparation Example 3 "Cation Electrodeposition Liquid Preparation Example" Using a cationic electrodeposition acrylic resin as a monomer, 30 parts by weight of methyl methacrylate, 30 parts by weight of ethyl acrylate, 30 parts by weight of 2-hydroxyethyl acrylate,
Using 20 parts by weight of N, N-dimethylaminopropylacrylamide, t-butyl peroctoate as an initiator, and butyl cellosolve as a solvent, the mixture was synthesized by a drop polymerization method at 120 ° C. to carry out pigment dispersion. An electrodeposition solution for red coloring was prepared by the following method. Acetic acid was excessively added so that the neutralization ratio became 110% with respect to the acrylic resin solid content of 30 parts by weight.
80 parts by weight of CI Pigment Red 177 and 20 parts by weight of CI Pigment Yellow 83 were mixed and dispersed using a sand mill for 10 hours. The dispersion was filtered under pressure, ion-exchanged water was added again to adjust the pigment concentration to 10%, and then acetonitrile was added to the electrodeposition solution to 15%. The electrodeposition solution for green coloring is 90 parts by weight of CI Pigment Green 36, CI Pigment Yellow 8
It was prepared in the same manner as the red coloring electrodeposition solution using 310 parts by weight. The electrodeposition solution for blue coloring was prepared in the same manner as the electrodeposition solution for red coloring using 80 parts by weight of CI Pigment Blue 16 and 20 parts by weight of CI Pigment Violet 23.

Preparation Example 4 "Preparation Example of Anion Electrodeposition Solution" An electrodeposition solution for red coloring was prepared by the following method. After mixing 17780 parts by weight of CI Pigment Red and 20 parts by weight of CI Pigment Yellow 83 with 30 parts by weight of a polycarboxylic acid-based polymer surfactant (Cariblon B manufactured by Sanyo Chemical Co., Ltd.) and 300 parts by weight of ion-exchanged water, a sand mill is used. 1
The dispersion was dispersed for 0 hours, and ion-exchanged water was added again to the dispersion filtered under pressure to adjust the pigment concentration to 10%.
Acetonitrile was added so as to be 15% in the electrodeposition solution. The electrodeposition liquid for green coloring is composed of 90 parts by weight of CI Pigment Green 36 and CI Pigment Yellow 83 10
It was prepared in the same manner as in the electrodeposition solution for red coloring using parts by weight. The electrodeposition solution for blue coloring is CI Pigment Blue 1
5 80 parts by weight, CI Pigment Violet 232
It was prepared in the same manner as the red coloring electrodeposition solution using 0 parts by weight.

Preparation Example 5 "Preparation Example of Anion Electrodeposition" Using an acrylic resin for anion electrodeposition as a monomer, 10 parts by weight of methacrylic acid, 30 parts by weight of methyl methacrylate, 20 parts by weight of lauryl methacrylate, 30 parts by weight of ethyl acrylate, 2-hydroxyethyl acrylate 20 parts by weight, t-butyl peroctoate as an initiator and butyl cellosolve as a solvent were synthesized at 120 ° C. by a drop polymerization method to carry out pigment dispersion. An electrodeposition solution for red coloring was prepared by the following method. Triethylamine was excessively added so that the neutralization ratio became 110% with respect to 30 parts by weight of the acrylic resin solid content, mixed and dissolved with 300 parts by weight of ion-exchanged water, and then CI Pigment Red 177 80 parts by weight, CI Pigment Yellow 83 20 parts by weight were mixed and dispersed using a sand mill for 10 hours. The dispersion is filtered under pressure, and ion-exchanged water is added again to reduce the pigment concentration to 10%.
Then, acetonitrile was added so as to be 15% in the electrodeposition solution. The electrodeposition solution for green coloring was prepared in the same manner as the electrodeposition solution for red coloring, using 90 parts by weight of CI Pigment Green 36 and 10 parts by weight of CI Pigment Yellow 83. The electrodeposition solution for blue coloring was prepared in the same manner as the electrodeposition solution for red coloring using 80 parts by weight of CI Pigment Blue 15 and 20 parts by weight of CI Pigment Violet 23.

Preparation Example 6 "Preparation Example of Micellar Electrolyte" A micellar electrolyte for red coloring was prepared by the following method. 150 parts by weight of lithium bromide and poly (oxyethylene)
After mixing 20 parts by weight of 11-ferrocenylundecyl ether with 500 parts by weight of ion-exchanged water, the mixture was dispersed using a sand mill for 1 hour, and further CI Pigment Red 177.
100 parts by weight were added and dispersed by a sand mill for 10 hours. Ion-exchanged water was added again to the dispersion filtered under pressure to adjust the pigment concentration to 10%, and acetonitrile was added to the electrolyte solution to 15%. The micellar electrolyte for green coloring is CI Pigment Green 7
It was prepared in the same manner as in the red coloring electrolyte using 100 parts by weight. The blue coloring micell electrolyte was prepared in the same manner as the red coloring electrolyte using 100 parts by weight of CI Pigment Blue 15.

Example 1 A 10% toluene solution of the polysilane obtained in Preparation Example 1 was spin-coated on a glass substrate (manufactured by Nisso Chemical Co., Ltd.) with a length of 5 cm × 5 cm × 0.11 cm in thickness. The coating was performed by using "PRS-14" manufactured by Dynapart. Subsequently, the coating film was dried to form a polysilane layer having a thickness of 1 μm. A quartz photomask in which a blue transmission pattern of a color filter is formed is superimposed on the obtained filter material, and the laminate is subjected to 2J using an ultra-high pressure mercury lamp parallel exposure apparatus (CL-50-200A manufactured by Nihon Battery Co., Ltd.). / Cm ² of UV light. After removing the photomask, the filter material on which the latent image was formed was immersed in the blue-colored electrodeposition solution of Preparation Example 2 to perform cation electrodeposition at 100 V for 10 seconds. After electrodeposition, wash with water
By drying at 10 ° C. for 10 minutes, a filter material colored in a blue pattern was obtained (first pattern electrodeposition step).
Next, using a photomask on which a red transmission pattern of a color filter was formed, blue and red were colored in the same manner as in the first pattern electrodeposition step except that the red coloring electrodeposition liquid of Preparation Example 2 was used. A filter material was obtained (second pattern electrodeposition step). Next, using a photomask on which a green transmission pattern of a color filter is formed, in the same manner as in the first pattern electrodeposition step, except that the green coloring electrodeposition liquid of Preparation Example 2 is used, coloring is performed in blue, red, and green. Color filters obtained
(Third pattern electrodeposition step).

Example 2 A color filter was obtained in the same manner as in Example 1 except that the cationic electrodeposition solution of Preparation Example 3 was used as the electrodeposition solution.

Example 3 The cationic electrodeposition solution of Preparation Example 3 was used as the electrodeposition solution, and an epoxy-urethane-based cationic electrodeposition coating material Powertop U-50 F-2 (manufactured by Nippon Paint Co., Ltd.) was used as a crosslinking agent component. Example 1 Example 1 except that it was mixed in the electrodeposition solution at a solid concentration of 5% and dried at 160 ° C. for 20 minutes.
A color filter was obtained in the same manner as described above.

Example 4 A color filter was obtained in the same manner as in Example 1 except that the anion electrodeposition solution of Preparation Example 4 was used as the electrodeposition solution, and that the anion electrodeposition was performed.

Example 5 A color filter was obtained in the same manner as in Example 1 except that the anion electrodeposition solution of Preparation Example 5 was used as the electrodeposition solution, and that the anion electrodeposition was performed.

Example 6 The anion electrodeposition solution of Preparation Example 5 was used as an electrodeposition solution, and an acrylic-melamine-based anion electrodeposition paint Power Mite 3000 (manufactured by Nippon Paint Co., Ltd.) was used as a crosslinking agent component at a solid content concentration. Mixing to 5% in the landing liquid,
A color filter was obtained in the same manner as in Example 1, except that the color filter was dried at 0 ° C. for 20 minutes.

Example 7 Using the micelle electrolyte of Preparation Example 6 as the electrodeposition solution,
A color filter was obtained in the same manner as in Example 1 except that micelle electrolysis was performed in the order of +1.5 (red), +1.2 V (green), and +0.9 V (blue). The color filters obtained in the steps of Examples 1 to 7 described above formed very good images without color mixing between the pixel patterns.

[Brief description of the drawings]

FIG. 1 is a process chart schematically showing the method of the present invention.

Continuation of front page (56) References YOKOYAMA ET. AL, CH EMISTRY LETTERS, JA PAN, THE CHEMICAL S OCIETY OF JAPAN, 1991, PP1563-1566 (58) Fields investigated (Int. Cl. ⁶ , DB names) G02B 5/20 101 G02F 1/1335 505

Claims (1)

(57) [Claims] A) a formula provided on a substrate via a transparent electrode layer (Wherein R ₁ , R ₂ , R ₃ and R ₄ are each independently selected from the group consisting of substituted or unsubstituted aliphatic hydrocarbon residues, alicyclic hydrocarbon residues and aromatic hydrocarbon residues. And m and n are integers.) A step of forming a latent image of a colored pattern by selectively irradiating a polysilane layer made of a polysilane having a structure represented by the formula: Dipping the polysilane layer on which the latent image is formed into an electrodepositable solution containing at least one dye or pigment, and electrodepositing the pattern to pattern-color the latent image portion; and c) the polysilane layer. Except that a latent image of a different colored pattern is formed, and that a different dye or pigment is used in the same manner as the pattern coloring step.
Forming a multicolored pattern on the polysilane layer, comprising: performing another pattern coloring step performed multiple times.